Electrodeposition of rare-earth elements from neodymium magnets using molten salt electrolysis

Rare-earth element is an important target for recycling in Japan. In our previous work, we demonstrated the selective leaching of rare-earth elements from waste neodymium magnets using chloride molten salt electrolysis. In this study, we investigated the electrodeposition of rare-earth elements using liquid metal as a cathode. The reduction potential obtained using a liquid-zinc electrode was higher than that obtained using a solid molybdenum electrode. A zinc–rare-earth alloy was formed as the electrodeposit. The total rare-earth element content of the electrodeposit was more than 99.8 mass% without zinc and other composition of electrolysis. The activity of rare-earth elements decreased upon alloy formation, suggesting that the oxidation rate of electrodeposited alloy will be decreased.     

Hydrometallurgical processing of Nd–Fe–B magnets for Nd purification

An evaluation of various metal purification processes subsequent to the leaching processing of the neodymium (Nd) product from neodymium–iron–boron (Nd–Fe–B) magnets has been conducted. These post-leaching purification processes included precipitation; replacement and electrolysis were studied in order to check the purity of the recovered neodymium. A hydrometallurgical investigation was adopted to digest the metal content of the scrap Nd–Fe–B magnets for the recovery of valuable Nd metal and other metals such as Fe, B, Co and Ni. The effect of leaching conditions such as solid-to-liquid ratio and temperature were optimized and 100 % Nd, 100 % Fe, 100 % B and 85.87 % Co leaching efficiencies were achieved under these conditions. The coating material of the magnet, Ni, achieved 50 % impregnation after increasing the reaction temperature to 70 °C. The metals present in the optimal leaching solution were recovered 99 % by pH adjustment. However, the replacement had the highest separation efficiency for the recovery of Nd metal. Further, the optimal leaching Nd–Fe–B solution was subjected to the electrolysis processes in order to verify the recovery efficiency for all metals.     

Scenario assessment of neodymium recycling in Japan based on substance flow analysis and future demand forecast

With the increasing demand for energy-saving technologies, neodymium-iron-boron magnets have been widely utilized in high-efficiency motors. However, the reserves of neodymium, which is a rare earth element (REE), are limited; thus, a strategy for scaling up the REE supply is highly required. In this study, a scenario assessment was conducted to evaluate the effect of material recycling of neodymium from final product waste. Domestic substance flow analysis of neodymium was conducted by focusing on the waste flow of the final product. Moreover, the demand and waste of neodymium until 2050 were forecasted using various multivariate analysis methods. The results showed that the domestic waste of neodymium was forecasted to be 3866–4217 tons/year by 2050. However, material recycling of neodymium from final product waste may cause an additional increase in production by “circular economy rebound”. Considering that CO₂ reduction has also been a global challenge to prevent global warming, the rebound effect was calculated. Therefore, a scenario assessment was conducted to evaluate the influence of this rebound effect by estimating the CO₂ reduction. The results of this study are expected to make a significant contribution to the establishment of a new strategy for neodymium recycling.

     

Scenario analysis for recovery of rare earth elements from end-of-life vehicles

End-of-life vehicles (ELVs) are increasingly being recognized as a possible future resource pool for rare earth elements (REEs). This study provides the amount of REEs that can be recovered from ELVs in Japan based on dismantling survey, chemical identification and substance flow analysis. The REEs were quantified from common passenger vehicles and hybrid electric vehicles. We targeted 17 REEs in estimation of REE contents in ELVs. Four scenarios were developed to explore the recovery of REEs from ELVs. In these scenarios, NiMH batteries and motors containing NdFeB magnets were identified as target components due to they are main REEs carriers; we focused on interpretation of neodymium (Nd) and dysprosium (Dy) owing to they are two of the most critical REEs. The results suggest that 2700 (±500) tons of REEs can be recovered, of which 520 (±100) tons and 31 (±7) tons will be contributed by Nd and Dy in 2030. Meanwhile, the Dy recovered from ELVs can satisfy 23 % (±6 %) of the demand for NdFeB magnets and NiMH battery cells in automobile production of Japan; the Nd recovered from ELVs can satisfy 49 % (±9 %) of the production demands.     

Impact of Cathode Conditions on Coupled Electrochemical Treatment of Nitrate Brine Concentrates

Simulated concentrated nitrate brine waste was treated in a two-stage electrolysis process, where reduction of nitrate in a cathodic chamber was coupled with oxidation of ammonium (produced in the previous stage) in an anodic chamber. The influence of operating conditions such as applied potential, electrolyte composition, and initial concentration on conversion of nitrate to ammonium in the cathodic chamber was investigated. The effects of chloride and current density on the two-stage treatment process were also examined. More negative potential at the cathode (?2.0 vs. ?1.7 and ?1.5 V) and higher current density (33 vs. 22 and 13.9 mA/cm²) favored ammonium as the product of nitrate reduction at a copper cathode and increased the overall amount of nitrate conversion. Faster reduction was seen when nitrate concentration was lower (0.01 vs. 0.02 N), but total mass conversion of nitrate in the same time period was higher for 0.02 N. The reduction of nitrate was not sensitive to sulfate or chloride concentration in the ranges studied (0–2 and 1–1.5 mg/L, respectively), but the oxidation of ammonium was noticeably higher when chloride was present. Only small amounts of ammonium and nitrate remained in the second-stage effluent after coupled treatment.     

我国腈纶废水物化预处理方法的研究进展

结合我国腈纶废水的特征,系统归纳了近年来我国腈纶废水常用物化预处理方法的研究进展。物化预处理方法包括内电解法、混凝法、Fenton氧化法、电解法、臭氧氧化法、光催化氧化法、微波法等。这些方法普遍存在高成本、高能耗、实际运行费用大等问题。对未来物化预处理方法的研究方向提出了建议。最后指出,腈纶废水的处理应朝着节能高效和资源化的方向发展,推动我国腈纶废水处理技术的不断进步和完善。     

电絮凝-过硫酸盐氧化协同工艺处理页岩气压裂返排废水

采用电絮凝-过硫酸盐氧化协同工艺处理页岩气压裂返排废水,通过电解过程产生的Fe2+活化过硫酸盐产生强氧化性的硫酸根自由基氧化废水中的有机物,同时Fe2+被氧化成Fe3+进而水解起到絮凝作用。实验结果表明,在电解时间25 min、电流密度41.7 m A/cm~2、电极间距4 cm、搅拌转速100 r/min、废水pH 7.0、过硫酸盐添加量0.006 mol/L的条件下,COD去除率达94.5%,出水BOD_5/COD从0.13增至0.56,电导率从104 mS/m降至71 mS/m,矿化度从16 704 mg/L降至4 065 mg/L,不可滤残渣含量从554 mg/L降至59 mg/L。电絮凝-过硫酸盐氧化协同处理的效果明显优于单独电絮凝和硫酸亚铁活化过硫酸盐氧化工艺,循环伏安测试结果表明其原因是硫酸根自由基的产生,同时溶液的导电性增强,强化了絮凝效果。     

染料废水的脱色方法

综述了染料废水的污染特征和混凝,电解、氧化、吸附、生物降解等各种脱色方法,分析了相应的脱色机理,并介绍了染料废水的组合处理方法。     

石墨毡电极预处理模拟邻甲酚废水

采用聚丙烯腈基石墨毡电极，以NaCl为电解质，在恒流电解的条件下，对质量浓度为1 000 mg/L、COD=3 672 mg/L的模拟邻甲酚废水进行预处理。研究了电解时间、初始废水pH、NaCl加入量、电流密度对邻甲酚去除率的影响，考察了废水的COD变化，并探讨了反应机理。实验结果表明：石墨毡电极具有较好的导电性、吸附性，对邻甲酚具有较好的电化学氧化性能;常温常压下，初始废水pH为6~7、电流密度为90 A/m2、向300 mL废水中加入0.5 g NaCl时，经4 h电解，邻甲酚的去除率达到97.1%，COD的去除率达到47.3%;处理后废水的BOD5/COD由0.04提高至0.33，可不经稀释直接进行生物处理。     

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used.The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks.The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks.Fluidized bed combustion was applied to char residues. Above 700 °C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO₂ during its oxidation was lower than for the parent coal, while for NO_X emissions, the trend was observed to increase NO_X formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.     

In situ hypochlorous acid generation for the treatment of syntan wastewater

A new treatment process was employed to treat wastewater generated from a factory manufacturing syntan (synthetic tannin). In this treatment process, in-situ production of hypochlorous acid was achieved by the use of an aqueous sodium chloride solution for chlorine production. As the graphite anode and stainless steel cathode zones were kept unseparated, the hypochlorous acid was produced by electrolysis. The hypochlorous acid was utilized for the oxidation of organic matter present in the wastewater. The results showed that for an initial COD concentration of 10,000 mg/l, a turbidity of 277 NTU, a tannin concentration of 4000 mg/l, a temperature of 27±1°C, a current density of 42.5 mA/cm², a sodium chloride content of 3% and an electrolysis period of 210 min showed an effluent COD concentration of 230 mg/l, a turbidity of 9 NTU, a tannin concentration below the detection limit and a temperature of 37±2°C.     

Degradability Characterization of EPDM/IIR Blends by γ-irradiation

In this paper the modifications induced in butyl rubbers (pristine, chlorinated and brominated sorts) by γ-irradiation are investigated by swelling, chemiluminescence and FT-IR. The susceptibility of butyl rubbers for the generation of radicals orders their stabilities in the following sequence: IIR?>?IIR—Cl?>?IIR—Br. The incorporation of butyl rubbers into ethylene-propylene terpolymer matrix brings about increased densities of radicals initiating modifications in the oxidation state in respect with recombination, which are intensified as the processing dose increases. Based on the variation of carbonyl and hydroxyl indices the favorable route for the recycling EPDM based formulations would be suggested in this study. The chemiluminescence spectra proving the formation of peroxyl radicals at about 100?°C prove their availability as reclaiming solutions. IIR—Br is the recommendable butyl rubber for the recovery procedure by association with EPDM. The suitability of IIRs for recycling purposes is analyzed by the variation in their crosslink densities, free volumes and swelling degrees. The crosslinking behavior of stabilized EPDM/IIR blends that runs to the improvement of durability is depicted by Charlesby–Pinner representation, which involves the different simultaneous contribution of scission and crosslinking processes.     

钛基金属氧化物电极的制备及性能

采用聚合物前驱体法制备了Ti/SnO₂-Sb₂O₃电极，再通过恒电流电沉积法制备了 Ti/SnO₂-Sb₂O₃/PbO₂和Ti/SnO₂-Sb₂O₃/MnO₂电极。采用SEM技术对3种金属氧化物电极表面的形貌进行了表征，并分别以3种电极为阳极进行了苯酚的电催化氧化实验。实验结果表明：电解时间为2.5 h时，Ti/SnO₂-Sb₂O₃电极、Ti/SnO₂-Sb₂O₃/PbO₂电极和Ti/SnO₂-Sb₂O₃/MnO₂电极对苯酚的降解率分别为85.9%，83.2%，44.6%；苯酚在3种电极上的电催化氧化反应均遵循一级反应动力学方程；苯酚在Ti/SnO₂-Sb₂O₃ 电极和Ti/SnO₂-Sb₂O₃/PbO₂电极上的反应速率较快，并具有较高的析氧电位；Ti/SnO₂-Sb₂O₃/PbO₂电极具有更好的耐腐蚀性和更长的使用寿命。     

A sustainable system for decontamination of cephalexin antibiotic using electrocoagulation technology and response surface methodology

The emergence of synthetic micropollutants in wastewater due to domestic and industrial use has presented new challenges for treatment processes. Among these pollutants, pharmaceutical and personal care products (PPCPs) are considered emerging contaminants due to their potential to enter drinking water sources. Antibiotics, in particular, are of significant concern due to their high consumption in veterinary and human applications. In this study, the electrocoagulation (EC) process is used as an efficient technique for the removal of cephalexin (CFX) from pharmaceutical wastewater. The study aims to explore the ability of the EC process to remove CFX and optimize its performance using the response surface method based on Central Composite Design (RSM-CCD). The effects of initial CFX concentration, electrolysis time, initial pH, and electrode type (non-insulated and insulated) were considered in the optimization process. This research is distinct as it examines the influence of key factors on the elimination of CFX. The results showed that electrolysis time had the most significant effect on CFX removal using the EC process. The analysis of variance (ANOVA) test was used to evaluate the importance of independent variables and their interaction. The optimal operating conditions for maximum removal efficiency (86.53%) were an initial CFX concentration, reaction time, and initial pH of 34 mg/L, 34.35 min, and 6.5, respectively, using an insulated electrode. Under these optimal conditions, predicted CFX removal was 93.54%. These findings demonstrate that RSM-CCD is a useful tool for optimizing electrochemical removal processes for micropollutants such as CFX from wastewater streams. The study highlights the importance of considering electrode type in optimizing EC processes for micropollutant removal from wastewater.     

高级氧化法处理光引发剂生产废水

分别采用臭氧氧化、微电解—Fenton氧化和电化学降解的方法处理COD为6 000~8 000 mg/L、BOD₅/ COD为 0.12~0.17的光引发剂生产废水,比较了3种方法对废水中COD的去除效果。实验结果表明：臭氧氧化反应2 h时废水COD去除率达35.9%,BOD₅/COD 为0.20;微电解反应4 h再Fenton氧化4 h后,废水COD去除率为38.2%,BOD₅/COD 为0.28;电化学降解2 h后废水COD去除率达83.9%,BOD₅/COD 为0.46,降解反应遵循零级反应动力学,反应速率常数为2.6 kg/（m³·h）。3种方法对光引发剂生产废水的处理效果顺序为：电化学降解>微电解—Fenton氧化>臭氧氧化。     

蒽醌修饰石墨毡电极预处理头孢合成废水

以钛涂钌电极为阳极、自制蒽醌修饰石墨毡电极为阴极,对头孢合成废水(COD=25 000~30 000 mg/L、ρ(NH3-N)=850~1 300 mg/L、色度为2 300~2 680度)进行了电化学氧化预处理,优化了电解条件,并对电化学体系的动力学和稳定性进行了分析。实验结果表明:蒽醌的存在可改善电化学氧化降解效果;在电解时间50 min、电流密度0.14 A/cm2、Na2SO4浓度0.1 mol/L、极板间距2 cm、初始废水p H 7.0的条件下,废水的COD、色度、NH3-N的去除率分别可达45.3%,66.9%,33.6%;BOD5/COD由处理前的0.27增至0.40,可生化性得到改善;COD、色度、NH3-N的电化学氧化降解过程均近似符合一级动力学方程;且该电化学体系的应用稳定性良好。     

Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Decolorization and estrogenic activity of colored livestock wastewater after electrolysis treatment

Livestock wastewater is treated by activated sludge treatment. Untreated livestock wastewater has high estrogen activity because animal excreta contains estrogen. When activated sludge treatment is applied, the estrogen activity declines or is lost. However, the color of treated livestock wastewater is deep brownish-red because of the decomposition of organic compounds or the synthesis of metabolites. Discharging colored wastewater to the environment could cause some problems, so it is necessary to decolorize colored wastewater before it is discharged. It has been suggested that electrolysis decolorization technology is suitable for treating colored wastewater; however, the process produces volatile organic compounds (VOCs). In fact, little research has been conducted with reference to estrogen activity in wastewater that has undergone electrolysis, especially on the contribution of the electrolysis decolorization process to estrogen activity, i.e., the possibility of resynthesis of some substance with estrogen activity due to resolved and metabolized colored components. In this study, the concentration of VOC was measured for various electrolysis conditions, and estrogen activity was examined using a yeast two-hybrid assay. From the results, decolorization of colored livestock wastewater by electrolysis was possible, and the VOC generation during electrolysis could be controlled depending on the electrolysis conditions. Estrogen activity in colored livestock wastewater disappeared on electrolysis decolorization.     

合成橡胶生产废水处理技术

分析了合成橡胶生产废水的水质特性，综述了混凝沉降、混凝气浮、生物处理、电解絮凝、吸附和反渗透等方法在橡胶废水处理方面的应用。     

Purification of spent cathode carbon from aluminum electrolysis cells by alkali fusion-acid leaching process

Journal of Material Cycles and Waste Management - Spent cathode carbon (SCC), with high recycling potential of carbon, is an unavoidable solid waste in the aluminum electrolysis industry. In this...