Pub Date : 2024-04-26DOI: 10.1007/s40831-024-00818-1
Zhen Zhang, Jue Tang, Mansheng Chu, Quan Shi, Chuanqiang Wang
At present, there were two main problems with the cooling plate slag-hanging: One was that the research on the slag-hanging mechanism of cooling plate was not deep, and the other was that the calculation process of the slag layer thickness with cooling plate was unreasonable. Based on ANSYS ‘birth–death element,’ a slag layer iterative cycle calculation method was designed, and the change of slag layer under different boundary conditions was analyzed. The gas temperature increased from 1200 to 1600 °C, and the slag layer decreased from 56 to 8 mm. When the gas temperature was 1550 °C, the copper cooling plate would exceeded safe operating temperature (120 °C). The thermal conductivity increased from 1.2 W·m2 °C−1 to 2.2 W·m2·°C−1, and the slag layer was able to be thickened by 76–85%; however, the slag layer would became non-uniform. When the temperature of slag-hanging increased by 50 °C, the slag layer increased by about 6.9 mm-7.6 mm, and the uniformity of slag layer increased by 10%. The maximum temperature of cooling plate could be reduced by 5°C–10°C when the cooling water speed increased by 1 m·s−1. The cooling water temperature was reduced by 10 °C, and the maximum temperature of cooling plate and the measuring point temperature could be reduced about 10 °C. The above research and analysis provided a basis for the blast furnace to have a reasonable operating furnace type and a longer life.
{"title":"Slag-Hanging Capacity of Numerical Simulation and Analysis of Blast Furnace Copper Cooling Plate Based on ANSYS ‘Birth–Death Element’","authors":"Zhen Zhang, Jue Tang, Mansheng Chu, Quan Shi, Chuanqiang Wang","doi":"10.1007/s40831-024-00818-1","DOIUrl":"https://doi.org/10.1007/s40831-024-00818-1","url":null,"abstract":"<p>At present, there were two main problems with the cooling plate slag-hanging: One was that the research on the slag-hanging mechanism of cooling plate was not deep, and the other was that the calculation process of the slag layer thickness with cooling plate was unreasonable. Based on ANSYS ‘birth–death element,’ a slag layer iterative cycle calculation method was designed, and the change of slag layer under different boundary conditions was analyzed. The gas temperature increased from 1200 to 1600 °C, and the slag layer decreased from 56 to 8 mm. When the gas temperature was 1550 °C, the copper cooling plate would exceeded safe operating temperature (120 °C). The thermal conductivity increased from 1.2 W·m<sup>2</sup> °C<sup>−1</sup> to 2.2 W·m<sup>2</sup>·°C<sup>−1</sup>, and the slag layer was able to be thickened by 76–85%; however, the slag layer would became non-uniform. When the temperature of slag-hanging increased by 50 °C, the slag layer increased by about 6.9 mm-7.6 mm, and the uniformity of slag layer increased by 10%. The maximum temperature of cooling plate could be reduced by 5°C–10°C when the cooling water speed increased by 1 m·s<sup>−1</sup>. The cooling water temperature was reduced by 10 °C, and the maximum temperature of cooling plate and the measuring point temperature could be reduced about 10 °C. The above research and analysis provided a basis for the blast furnace to have a reasonable operating furnace type and a longer life.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"18 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140798320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-18DOI: 10.1007/s40831-024-00822-5
Aparna Sai Surya Sree Nedunuri, Salman Muhammad
Alkali-activated materials are one of the alternative cementitious materials, but their extensive usage is constrained by certain limitations, such as quick setting and rapid loss of workability. By addressing these limitations, this study developed alkali-activated concrete formulations, with enhanced workable times and pumpable workability, comprising of precursors based on fly ash and blast furnace slag. The precursors were activated with sodium silicate activator of molar modulus 1.5 and activator dosage (% of Na2O) of 8 and 10%. Zinc sulfate was incorporated as a retarder to prolong the workable times. The spread diameter of these concrete mixtures measured at 10th min was in the range of 650–745 mm. Several of the developed concrete mixtures could retain the spread diameters in the range of 430 – 655 mm for a duration longer than 90 min. These developed alkali-activated concrete mixtures with pumpable workability and prolonged workable times have exhibited compressive strengths in the range of M30 to M60 grade. The rheological behavior of these concrete mixtures was also assessed on their corresponding concrete equivalent mortar (CEM) mixtures. The yield stress and plastic viscosity of CEM mixtures were found to decrease with an increase in the proportion of fly ash and increase with an increase in the hydration time and retarder content. The evolution of yield stress and plastic viscosity of alkali-activated CEM mixtures were found to be in agreement with the obtained spread diameter values for concrete mixtures.
{"title":"Development of Sodium Silicate-Activated Ground Granulated Blast Furnace Slag and Fly Ash Binder-Based Concrete for Pumping Applications","authors":"Aparna Sai Surya Sree Nedunuri, Salman Muhammad","doi":"10.1007/s40831-024-00822-5","DOIUrl":"https://doi.org/10.1007/s40831-024-00822-5","url":null,"abstract":"<p>Alkali-activated materials are one of the alternative cementitious materials, but their extensive usage is constrained by certain limitations, such as quick setting and rapid loss of workability. By addressing these limitations, this study developed alkali-activated concrete formulations, with enhanced workable times and pumpable workability, comprising of precursors based on fly ash and blast furnace slag. The precursors were activated with sodium silicate activator of molar modulus 1.5 and activator dosage (% of Na<sub>2</sub>O) of 8 and 10%. Zinc sulfate was incorporated as a retarder to prolong the workable times. The spread diameter of these concrete mixtures measured at 10th min was in the range of 650–745 mm. Several of the developed concrete mixtures could retain the spread diameters in the range of 430 – 655 mm for a duration longer than 90 min. These developed alkali-activated concrete mixtures with pumpable workability and prolonged workable times have exhibited compressive strengths in the range of M30 to M60 grade. The rheological behavior of these concrete mixtures was also assessed on their corresponding concrete equivalent mortar (CEM) mixtures. The yield stress and plastic viscosity of CEM mixtures were found to decrease with an increase in the proportion of fly ash and increase with an increase in the hydration time and retarder content. The evolution of yield stress and plastic viscosity of alkali-activated CEM mixtures were found to be in agreement with the obtained spread diameter values for concrete mixtures.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"27 1 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140629720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Monosilane (SiH4) is a common precursor for the production of high-purity silicon for solar PV applications. As an alternative to carbothermic reduction of silica to produce metallurgical grade silicon with subsequent conversion to silane, an alternative route over magnesiothermic reduction of silica to Mg2Si has been explored in our earlier work. In the current work, silane gas production through hydrolysis of Mg2Si in HCl acid solution was studied. Two sources of Mg2Si were chosen: a commercial Mg2Si source and a Mg2Si source produced through magnesiothermic reduction of high-purity natural quartz. Effects of various parameters on the hydrolysis of Mg2Si, including different experimental setups, temperature of the acid solution, acid concentration, reaction time, and relative amounts of reactants were studied. The evolution of produced gases was determined by two different methods: firstly, by passing the produced gas through a KOH solution to capture Si with subsequent analysis of the Si content in the KOH solution by inductively coupled plasma mass spectrometry and secondly, on-line gas analysis by GC–MS. The silane distribution between different silane species with reaction time was evaluated and the activation energy of silane formation was calculated. The results indicated comparable silane yields obtained from the on-line GC–MS method and KOH solution analysis method, as well as for commercial Mg2Si and the Mg2Si–MgO mixture produced through magnesiothermic reduction. Furthermore, adding HCl acid to Mg2Si in water led to higher SiH4 formation yield than adding Mg2Si to acid. However, the total silane yield for the two methods was similar at approximately 32%.
{"title":"Silane Gas Production Through Hydrolysis of Magnesium Silicide by Hydrochloric Acid","authors":"Azam Rasouli, Raphael Kuhn, Samson Yuxiu Lai, Jafar Safarian, Gabriella Tranell","doi":"10.1007/s40831-024-00817-2","DOIUrl":"https://doi.org/10.1007/s40831-024-00817-2","url":null,"abstract":"<p>Monosilane (SiH<sub>4</sub>) is a common precursor for the production of high-purity silicon for solar PV applications. As an alternative to carbothermic reduction of silica to produce metallurgical grade silicon with subsequent conversion to silane, an alternative route over magnesiothermic reduction of silica to Mg<sub>2</sub>Si has been explored in our earlier work. In the current work, silane gas production through hydrolysis of Mg<sub>2</sub>Si in HCl acid solution was studied. Two sources of Mg<sub>2</sub>Si were chosen: a commercial Mg<sub>2</sub>Si source and a Mg<sub>2</sub>Si source produced through magnesiothermic reduction of high-purity natural quartz. Effects of various parameters on the hydrolysis of Mg<sub>2</sub>Si, including different experimental setups, temperature of the acid solution, acid concentration, reaction time, and relative amounts of reactants were studied. The evolution of produced gases was determined by two different methods: firstly, by passing the produced gas through a KOH solution to capture Si with subsequent analysis of the Si content in the KOH solution by inductively coupled plasma mass spectrometry and secondly, on-line gas analysis by GC–MS. The silane distribution between different silane species with reaction time was evaluated and the activation energy of silane formation was calculated. The results indicated comparable silane yields obtained from the on-line GC–MS method and KOH solution analysis method, as well as for commercial Mg<sub>2</sub>Si and the Mg<sub>2</sub>Si–MgO mixture produced through magnesiothermic reduction. Furthermore, adding HCl acid to Mg<sub>2</sub>Si in water led to higher SiH<sub>4</sub> formation yield than adding Mg<sub>2</sub>Si to acid. However, the total silane yield for the two methods was similar at approximately 32%.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"127 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140613083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-15DOI: 10.1007/s40831-024-00826-1
Yang Qu, Hongjie Luo, Zekun Zhi, Jinbo Qiao, Linli Wu
The growing scarcity of conventional oil resources has intensified the focus on shale oil, known for its abundant reserves. Nevertheless, in the process of shale oil retorting, a substantial quantity of harmful waste oil shale residue (OSR) is generated. In this study, OSR and bituminous coal sourced from Fushun City served as the raw materials for the production of Si–Al–Fe alloy in a DC electric arc furnace, proposing a novel way to efficiently utilize OSR. The experiment summarized and analyzed the current oxide reduction theory, combined with the actual experimental results, focused on investigating the phase transformations of OSR during the reduction process. Based on the gaseous suboxide-carbide reaction theory, the reduction mechanism of pellet raw materials at high temperature was proposed. Results showed that the pellet raw materials will first undergo high temperature decomposition during the reduction process, and generated a large amount of carbides. Carbides subsequently reacted with metal suboxides produced in the high-temperature zone of the electric arc furnace to yield alloys. The element distribution of the obtained alloy product was non-uniform, the metallic Si phase was closely adjacent to the SiC substance, and the Fe in the alloy significantly enriched the reduced Al and Ti elements.
Graphical Abstract
传统石油资源的日益匮乏使人们更加关注储量丰富的页岩油。然而，页岩油在蒸馏过程中会产生大量有害的废油页岩渣（OSR）。本研究以抚顺市的油页岩残渣和烟煤为原料，在直流电弧炉中生产硅-铝-铁合金，提出了一种高效利用油页岩残渣的新方法。实验总结分析了现有的氧化还原理论，结合实际实验结果，重点研究了氧化还原过程中氧化还原剂的相变。基于气态亚氧化物-碳化物反应理论，提出了球团原料在高温下的还原机理。结果表明，球团原料在还原过程中首先会发生高温分解，生成大量碳化物。碳化物随后与电弧炉高温区产生的金属亚氧化物反应生成合金。所得合金产品的元素分布不均匀，金属 Si 相紧邻 SiC 物质，合金中的 Fe 显著富集了还原的 Al 和 Ti 元素。
{"title":"Carbothermal Reduction of Oil Shale Residue (OSR) in DC Electric Furnace to Prepare Si–Al–Fe Alloy","authors":"Yang Qu, Hongjie Luo, Zekun Zhi, Jinbo Qiao, Linli Wu","doi":"10.1007/s40831-024-00826-1","DOIUrl":"https://doi.org/10.1007/s40831-024-00826-1","url":null,"abstract":"<p>The growing scarcity of conventional oil resources has intensified the focus on shale oil, known for its abundant reserves. Nevertheless, in the process of shale oil retorting, a substantial quantity of harmful waste oil shale residue (OSR) is generated. In this study, OSR and bituminous coal sourced from Fushun City served as the raw materials for the production of Si–Al–Fe alloy in a DC electric arc furnace, proposing a novel way to efficiently utilize OSR. The experiment summarized and analyzed the current oxide reduction theory, combined with the actual experimental results, focused on investigating the phase transformations of OSR during the reduction process. Based on the gaseous suboxide-carbide reaction theory, the reduction mechanism of pellet raw materials at high temperature was proposed. Results showed that the pellet raw materials will first undergo high temperature decomposition during the reduction process, and generated a large amount of carbides. Carbides subsequently reacted with metal suboxides produced in the high-temperature zone of the electric arc furnace to yield alloys. The element distribution of the obtained alloy product was non-uniform, the metallic Si phase was closely adjacent to the SiC substance, and the Fe in the alloy significantly enriched the reduced Al and Ti elements.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"213 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140589406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-09DOI: 10.1007/s40831-024-00803-8
Sen Zhou, Mouhamadou A. Diop, Bingliang Gao, Zhaowen Wang, Xianwei Hu, Youjian Yang, Wenju Tao
The present study investigates the impact of erosion holes and subsequent repairs on the current distribution at the cathode-metal interface in aluminum reduction cells. The research focuses on examining the effects of erosion hole location, size, repair material properties, and the modification of cathode collector bars to optimize cathode repair strategies. The findings indicate that erosion holes lead to a localized concentration of current distribution in the metal at the erosion site. Notably, the maximum current density observed reaches 46125 A/m2, and the maximum horizontal current in the lateral cell direction at the cathode-metal interface increases with the depth of the erosion hole. Furthermore, the study reveals that the electrical conductivity of repair materials significantly influences current distribution. Materials with high resistivity behave similarly to insulators. Post-repair actions, including the cutting off of the collector bar, result in a noticeable reduction in current density, with a maximum horizontal current of 5860 A/m2. These results provide valuable insights into optimizing cathode repair processes, offering implications for enhancing aluminum reduction cells' efficiency, productivity, and cost-effectiveness.
{"title":"Enhancing Sustainability in Aluminum Reduction Cells Through Cathode Repair Optimization and Numerical Simulations Study on Current Distribution and Erosion Hole Impact","authors":"Sen Zhou, Mouhamadou A. Diop, Bingliang Gao, Zhaowen Wang, Xianwei Hu, Youjian Yang, Wenju Tao","doi":"10.1007/s40831-024-00803-8","DOIUrl":"https://doi.org/10.1007/s40831-024-00803-8","url":null,"abstract":"<p>The present study investigates the impact of erosion holes and subsequent repairs on the current distribution at the cathode-metal interface in aluminum reduction cells. The research focuses on examining the effects of erosion hole location, size, repair material properties, and the modification of cathode collector bars to optimize cathode repair strategies. The findings indicate that erosion holes lead to a localized concentration of current distribution in the metal at the erosion site. Notably, the maximum current density observed reaches 46125 A/m<sup>2</sup>, and the maximum horizontal current in the lateral cell direction at the cathode-metal interface increases with the depth of the erosion hole. Furthermore, the study reveals that the electrical conductivity of repair materials significantly influences current distribution. Materials with high resistivity behave similarly to insulators. Post-repair actions, including the cutting off of the collector bar, result in a noticeable reduction in current density, with a maximum horizontal current of 5860 A/m<sup>2</sup>. These results provide valuable insights into optimizing cathode repair processes, offering implications for enhancing aluminum reduction cells' efficiency, productivity, and cost-effectiveness.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"77 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140602670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this paper, we respectively added 5 wt% of Na2O and CaCl2 to the CaO–MgO–Al2O3–SiO2 base glass, aiming to analyze the effect of the types of flux, CaCl2, and traditional flux Na2O, on the crystallization behavior and mechanical properties of the sintered glass–ceramics. Besides, 1 wt% of Cr2O3 was added as the nucleating agent to form the Cr-spinel nucleus and promote the bulk crystallization. The CaCl2-bearing glass–ceramics (GC-Cl) showed lower porosity and crystallinity compared with the Na2O-bearing glass–ceramics (GC-Na). After sintering at 950 °C for 1 h, the bending strength, Vickers hardness, and fracture toughness of GC-Cl were 163 MPa, 6.9 GPa, and 2.4 MPa·m1/2, respectively, while they are 191 MPa, 8.2 GPa, and 2.3 MPa·m1/2 for the GC-Na. Although the bending strength and hardness of GC-Cl are lower than that of GC-Na, adding CaCl2 as a flux may provide a route for the comprehensive utilization of CaCl2-bearing wastes.
{"title":"Effects of Na2O and CaCl2 on the Crystallization and Mechanical Properties of CaO-MgO-Al2O3-SiO2 Glass–Ceramics","authors":"Hong-Yang Wang, Yu Li, Shu-Qiang Jiao, Guo-Hua Zhang","doi":"10.1007/s40831-024-00819-0","DOIUrl":"https://doi.org/10.1007/s40831-024-00819-0","url":null,"abstract":"<p>In this paper, we respectively added 5 wt% of Na<sub>2</sub>O and CaCl<sub>2</sub> to the CaO–MgO–Al<sub>2</sub>O<sub>3</sub>–SiO<sub>2</sub> base glass, aiming to analyze the effect of the types of flux, CaCl<sub>2</sub>, and traditional flux Na<sub>2</sub>O, on the crystallization behavior and mechanical properties of the sintered glass–ceramics. Besides, 1 wt% of Cr<sub>2</sub>O<sub>3</sub> was added as the nucleating agent to form the Cr-spinel nucleus and promote the bulk crystallization. The CaCl<sub>2</sub>-bearing glass–ceramics (GC-Cl) showed lower porosity and crystallinity compared with the Na<sub>2</sub>O-bearing glass–ceramics (GC-Na). After sintering at 950 °C for 1 h, the bending strength, Vickers hardness, and fracture toughness of GC-Cl were 163 MPa, 6.9 GPa, and 2.4 MPa·m<sup>1/2</sup>, respectively, while they are 191 MPa, 8.2 GPa, and 2.3 MPa·m<sup>1/2</sup> for the GC-Na. Although the bending strength and hardness of GC-Cl are lower than that of GC-Na, adding CaCl<sub>2</sub> as a flux may provide a route for the comprehensive utilization of CaCl<sub>2</sub>-bearing wastes.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"33 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140589630","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-08DOI: 10.1007/s40831-024-00815-4
Nand Peeters, Sofía Riaño, Koen Binnemans
A significant consequence of the green transition is the growing demand of lithium-ion batteries (LIBs), as they are essential for electrical vehicles. In turn, the demand for the raw materials that are needed to produce LIBs is increasing. A common LIB cathode type for electrical cars is lithium nickel manganese cobalt oxide (NMC). Since cobalt is currently considered as a critical raw material, nickel-rich NMC cathodes are now designed with lower cobalt contents. The synthesis of these new NMC types requires LiOH instead of Li2CO3, which was used for Co-richer NMC materials in the past. Most production routes of LiOH start from Li2CO3 or Li2SO4. However, LiCl could also be a potential precursor for LiOH, as it could be obtained from various lithium sources. A two-step solvent extraction process (SX) was developed for direct conversion of LiCl into LiOH, using a phenol (butylhydroxytoluene or BHT) and a mixture of quaternary ammonium chlorides (Aliquat 336) in an aliphatic diluent (Shellsol D70) as the solvent. The SX process was validated in counter-current mode using a rotary agitated Kühni extraction column. The use of a column instead of mixer-settlers reduced the CO2 uptake by the final product (LiOH), which prevented the partial conversion of LiOH to Li2CO3. A total of 75 L of LiCl feed solution was processed in the Kühni column to obtain a solution of LiOH with a final purity of more than 99.95%, at a yield of 96%.
{"title":"Conversion of Lithium Chloride into Lithium Hydroxide Using a Two-Step Solvent Extraction Process in an Agitated Kühni Column","authors":"Nand Peeters, Sofía Riaño, Koen Binnemans","doi":"10.1007/s40831-024-00815-4","DOIUrl":"https://doi.org/10.1007/s40831-024-00815-4","url":null,"abstract":"<p>A significant consequence of the green transition is the growing demand of lithium-ion batteries (LIBs), as they are essential for electrical vehicles. In turn, the demand for the raw materials that are needed to produce LIBs is increasing. A common LIB cathode type for electrical cars is lithium nickel manganese cobalt oxide (NMC). Since cobalt is currently considered as a critical raw material, nickel-rich NMC cathodes are now designed with lower cobalt contents. The synthesis of these new NMC types requires LiOH instead of Li<sub>2</sub>CO<sub>3</sub>, which was used for Co-richer NMC materials in the past. Most production routes of LiOH start from Li<sub>2</sub>CO<sub>3</sub> or Li<sub>2</sub>SO<sub>4</sub>. However, LiCl could also be a potential precursor for LiOH, as it could be obtained from various lithium sources. A two-step solvent extraction process (SX) was developed for direct conversion of LiCl into LiOH, using a phenol (butylhydroxytoluene or BHT) and a mixture of quaternary ammonium chlorides (Aliquat 336) in an aliphatic diluent (Shellsol D70) as the solvent. The SX process was validated in counter-current mode using a rotary agitated Kühni extraction column. The use of a column instead of mixer-settlers reduced the CO<sub>2</sub> uptake by the final product (LiOH), which prevented the partial conversion of LiOH to Li<sub>2</sub>CO<sub>3</sub>. A total of 75 L of LiCl feed solution was processed in the Kühni column to obtain a solution of LiOH with a final purity of more than 99.95%, at a yield of 96%.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"213 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140589824","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-08DOI: 10.1007/s40831-024-00814-5
Rafael Piumatti de Oliveira, Jonathan Tenório Vinhal, Luciana Harue Yamane, Marcela dos Passos Galluzzi Baltazar, Denise Crocce Romano Espinosa
Literature regarding metals recovery from LED waste mainly focuses on semiconductor materials and precious metals, lacking data about rare earth elements. This paper explores this gap presenting an experimental study of yttrium extraction from LED waste by alkali fusion/acid leaching method. For this purpose, LED samples were obtained from tubular lamp. Chemical and thermal analyses were performed. Alkali fusion preprocessing was adopted followed by nitric acid leaching to solve difficult yttrium extraction from aluminate structure of LED phosphor. A chemical reaction mechanism in the alkali fusion involving degradation of the silicone polymer and destruction of the aluminate phosphor has been proposed as a novel approach to the subsequent easy leaching of rare earths from LED waste. Fusion conditions were 700 °C, for 3 h, NaOH/LED relation 1:1. Leaching solutions and solid residue were analyzed by energy dispersive X-ray fluorescence spectrometry, induced coupled plasma optical emission spectrometry, X-ray diffractometry and Fourier transform infrared spectroscopy. It was observed the undesirable formation of silica gel in the leaching liquor processed in temperatures below 70 °C. In that way, it is recommended the leaching at 90 °C, with formation of insoluble SiO2. Optimal leaching conditions found were leaching time of 20 min, 1/20 solid/liquid ratio, with 91% yttrium extraction in HNO3 2.5 mol/L at 90 °C.
Graphical Abstract
有关从 LED 废料中回收金属的文献主要集中在半导体材料和贵金属方面，缺乏有关稀土元素的数据。本文针对这一空白，介绍了通过碱熔/酸浸法从 LED 废料中提取钇的实验研究。为此，我们从管状灯中提取了 LED 样品。进行了化学和热分析。采用碱熔融预处理后硝酸浸出的方法，解决了从 LED 荧光粉的铝酸盐结构中提取钇的难题。提出了碱熔合过程中硅聚合物降解和铝酸盐荧光粉破坏的化学反应机制，作为随后从 LED 废料中轻松浸出稀土的新方法。熔解条件为 700 °C，持续 3 小时，NaOH/LED 比例为 1:1。通过能量色散 X 射线荧光光谱法、诱导耦合等离子体光发射光谱法、X 射线衍射法和傅立叶变换红外光谱法对浸出液和固体残留物进行了分析。结果表明，在低于 70 °C 的温度下处理的浸出液中会形成不理想的硅胶。因此，建议在 90 °C 下进行沥滤，以形成不溶性的二氧化硅。最佳浸出条件是浸出时间为 20 分钟，固液比为 1/20，在 2.5 摩尔/升的 HNO3 溶液中，钇的萃取率为 91%。
{"title":"Extraction of Yttrium from Light-Emitting Diode Waste by Alkali Fusion Followed by Acid Leaching","authors":"Rafael Piumatti de Oliveira, Jonathan Tenório Vinhal, Luciana Harue Yamane, Marcela dos Passos Galluzzi Baltazar, Denise Crocce Romano Espinosa","doi":"10.1007/s40831-024-00814-5","DOIUrl":"https://doi.org/10.1007/s40831-024-00814-5","url":null,"abstract":"<p>Literature regarding metals recovery from LED waste mainly focuses on semiconductor materials and precious metals, lacking data about rare earth elements. This paper explores this gap presenting an experimental study of yttrium extraction from LED waste by alkali fusion/acid leaching method. For this purpose, LED samples were obtained from tubular lamp. Chemical and thermal analyses were performed. Alkali fusion preprocessing was adopted followed by nitric acid leaching to solve difficult yttrium extraction from aluminate structure of LED phosphor. A chemical reaction mechanism in the alkali fusion involving degradation of the silicone polymer and destruction of the aluminate phosphor has been proposed as a novel approach to the subsequent easy leaching of rare earths from LED waste. Fusion conditions were 700 °C, for 3 h, NaOH/LED relation 1:1. Leaching solutions and solid residue were analyzed by energy dispersive X-ray fluorescence spectrometry, induced coupled plasma optical emission spectrometry, X-ray diffractometry and Fourier transform infrared spectroscopy. It was observed the undesirable formation of silica gel in the leaching liquor processed in temperatures below 70 °C. In that way, it is recommended the leaching at 90 °C, with formation of insoluble SiO<sub>2</sub>. Optimal leaching conditions found were leaching time of 20 min, 1/20 solid/liquid ratio, with 91% yttrium extraction in HNO<sub>3</sub> 2.5 mol/L at 90 °C.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"162 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140589629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-28DOI: 10.1007/s40831-024-00809-2
Lingbo Li, Li Zhou, Chenhui Liu, Yingwei Li, Jiyun Gao
Antimony is often used as a hardener for alloys. There are few studies on the preparation of antimony from Sb2O3 by microwave carbothermal reduction. In this study, Sb2O3 was used as the raw material, and the resonant cavity perturbation method was used to select anthracite as the reducing agent according to the microwave absorption of the material mixture. The single-factor experiment of reduction temperature, reduction time, and reducing agent ratio was carried out in a microwave tube furnace. The process parameters were optimized by response surface methodology (RSM). Under the optimized conditions, the reduction temperature was 758 °C, the reduction time was 56 min, the reducing agent addition ratio was 0.123, and the molten salt addition ratio was 0.1. An antimony ingot with a yield of 92.19% and a purity of 99.45% was obtained. The products and residue of the antimony ingot were analyzed by X-ray diffraction analysis (XRD), X-ray fluorescence (XRF), thermogravimetric (TG) analysis, scanning electron microscopy (SEM), and the mechanism of carbothermal reduction of antimony oxide powder in a microwave field was studied. The results showed that the microwave carbothermal reduction process of Sb2O3 under a microwave field had three stages: 25~655 °C, 655~850 °C, and >850 °C. Different stages changed with temperature. This green and energy-saving microwave heating technology can provide a feasible method for the efficient preparation of antimony.
{"title":"Preparation of Antimony Metal by Carbothermal Reduction of Antimony Oxide Powder in a Microwave Field: Mechanism and Process","authors":"Lingbo Li, Li Zhou, Chenhui Liu, Yingwei Li, Jiyun Gao","doi":"10.1007/s40831-024-00809-2","DOIUrl":"https://doi.org/10.1007/s40831-024-00809-2","url":null,"abstract":"<p>Antimony is often used as a hardener for alloys. There are few studies on the preparation of antimony from Sb<sub>2</sub>O<sub>3</sub> by microwave carbothermal reduction. In this study, Sb<sub>2</sub>O<sub>3</sub> was used as the raw material, and the resonant cavity perturbation method was used to select anthracite as the reducing agent according to the microwave absorption of the material mixture. The single-factor experiment of reduction temperature, reduction time, and reducing agent ratio was carried out in a microwave tube furnace. The process parameters were optimized by response surface methodology (RSM). Under the optimized conditions, the reduction temperature was 758 °C, the reduction time was 56 min, the reducing agent addition ratio was 0.123, and the molten salt addition ratio was 0.1. An antimony ingot with a yield of 92.19% and a purity of 99.45% was obtained. The products and residue of the antimony ingot were analyzed by X-ray diffraction analysis (XRD), X-ray fluorescence (XRF), thermogravimetric (TG) analysis, scanning electron microscopy (SEM), and the mechanism of carbothermal reduction of antimony oxide powder in a microwave field was studied. The results showed that the microwave carbothermal reduction process of Sb<sub>2</sub>O<sub>3</sub> under a microwave field had three stages: 25~655 °C, 655~850 °C, and >850 °C. Different stages changed with temperature. This green and energy-saving microwave heating technology can provide a feasible method for the efficient preparation of antimony.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"13 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140322241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-03-25DOI: 10.1007/s40831-024-00811-8
Kağan Benzeşik, Onuralp Yücel
The study investigates the combustion-assisted synthesis of lithium orthosilicate (Li4SiO4) powders for potential CO2 capture applications. Technical-grade lithium carbonate and metallic silicon powders were used as starting materials. Synthesis conditions were explored across temperatures ranging from 500 to 900 °C and different holding durations. Thermodynamic modeling using FactSage 8.2 software suggested that Li4SiO4 production is feasible at temperatures of 700 °C and higher with metallic silicon as the silicon source, which was confirmed experimentally. Characterization of the synthesized powders involved X-ray diffraction, specific surface area determination, particle size distribution analysis, scanning electron microscopy, and CO2 uptake tests. Despite having the lowest Li4SiO4 content as 83.7%, the sample synthesized at 700 °C with 45 min of holding time showed the best CO2 uptake performance as 12.80 wt% while having the lowest crystallite size value (126.58 nm), the highest specific surface area value (4.975 m2/g) and the lowest average particle size value (10.85 µm) which are highly effective on the CO2 uptake performance of such solid sorbents. The study concludes that while challenges remain in achieving optimal CO2 capture performance, it lays a foundation for utilizing lithium orthosilicate in carbon capture applications.
Graphical Abstract
该研究调查了燃烧辅助合成正硅酸锂（Li4SiO4）粉末的方法，该方法具有捕获二氧化碳的潜在应用价值。研究使用工业级碳酸锂和金属硅粉末作为起始材料。在 500 至 900 °C 的温度范围内和不同的保温时间内对合成条件进行了探索。使用 FactSage 8.2 软件进行的热力学建模表明，以金属硅作为硅源，在 700 ℃ 或更高温度下生产 Li4SiO4 是可行的，实验证实了这一点。合成粉末的表征包括 X 射线衍射、比表面积测定、粒度分布分析、扫描电子显微镜和二氧化碳吸收测试。尽管 Li4SiO4 的含量最低，仅为 83.7%，但在 700 °C 和 45 分钟保温时间下合成的样品显示出最佳的二氧化碳吸收性能（12.80 wt%），同时具有最低的结晶粒度值（126.58 nm）、最高的比表面积值（4.975 m2/g）和最低的平均粒度值（10.85 µm），这对此类固体吸附剂的二氧化碳吸收性能非常有效。研究得出结论，虽然在实现最佳二氧化碳捕集性能方面仍存在挑战，但它为在碳捕集应用中使用正硅酸锂奠定了基础。 图文摘要
{"title":"Thermodynamic Investigations for Combustion-Assisted Synthesis of Lithium Orthosilicate Powders","authors":"Kağan Benzeşik, Onuralp Yücel","doi":"10.1007/s40831-024-00811-8","DOIUrl":"https://doi.org/10.1007/s40831-024-00811-8","url":null,"abstract":"<p>The study investigates the combustion-assisted synthesis of lithium orthosilicate (Li<sub>4</sub>SiO<sub>4</sub>) powders for potential CO<sub>2</sub> capture applications. Technical-grade lithium carbonate and metallic silicon powders were used as starting materials. Synthesis conditions were explored across temperatures ranging from 500 to 900 °C and different holding durations. Thermodynamic modeling using FactSage 8.2 software suggested that Li<sub>4</sub>SiO<sub>4</sub> production is feasible at temperatures of 700 °C and higher with metallic silicon as the silicon source, which was confirmed experimentally. Characterization of the synthesized powders involved X-ray diffraction, specific surface area determination, particle size distribution analysis, scanning electron microscopy, and CO<sub>2</sub> uptake tests. Despite having the lowest Li<sub>4</sub>SiO<sub>4</sub> content as 83.7%, the sample synthesized at 700 °C with 45 min of holding time showed the best CO<sub>2</sub> uptake performance as 12.80 wt% while having the lowest crystallite size value (126.58 nm), the highest specific surface area value (4.975 m<sup>2</sup>/g) and the lowest average particle size value (10.85 µm) which are highly effective on the CO<sub>2</sub> uptake performance of such solid sorbents. The study concludes that while challenges remain in achieving optimal CO<sub>2</sub> capture performance, it lays a foundation for utilizing lithium orthosilicate in carbon capture applications.</p><h3 data-test=\"abstract-sub-heading\">Graphical Abstract</h3>\u0000","PeriodicalId":17160,"journal":{"name":"Journal of Sustainable Metallurgy","volume":"65 1","pages":""},"PeriodicalIF":2.4,"publicationDate":"2024-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140301867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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