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Using nanosecond laser pulses to debond the glass-EVA layer from silicon photovoltaic modules 使用纳秒激光脉冲使硅光电模块的玻璃-EVA 层脱落。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-30 DOI: 10.1016/j.wasman.2024.07.013

The active silicon cell of a solar photovoltaic (PV) panel is covered by an ethylenevinylacetate (EVA) adhesive and a protective top glass layer. Separating this glass-EVA layer from the underlying silicon represents a bottleneck for recycling PV panels. Previous work has shown that the EVA-Si bond can be weakened by applying a continuous source of heat to melt the EVA. In this paper, a new method using nanosecond laser pulses is demonstrated to induce transient melting selectively at the EVA-Si interface. This impulsive heating method can cleanly separate the glass-EVA layer from the silicon in both model and commercial multicrystalline PV panels. The dependence of this debonding on parameters like laser pulse fluence (laser pulse energy per area), wavelength, applied pressure, and scan speed were characterized. For model PV panels, the single-pulse laser fluences required for spontaneous separation of the assembly under the force of gravity, were 0.23, 0.32 and 0.78 J/cm2 for 355 nm, 532 nm and 1064 nm, respectively. The use of shorter wavelengths reduces the laser fluence needed for debonding, while higher fluences can compensate for faster laser beam scanning rates. Optical and electron microscopy images of the Si surfaces before and after laser irradiation show that the textured antireflection layer is destroyed but the silver metal grid remains intact. Preliminary experiments using 532 nm pulses showed that the laser debonding method could remove the glass-EVA layer from sections of decommissioned commercial PV panels, even when the top glass layer was densely cracked.

太阳能光伏(PV)电池板的活性硅电池由乙烯乙酸乙烯酯(EVA)粘合剂和顶部玻璃保护层覆盖。将玻璃-EVA 层与底层硅分离是回收光伏板的一个瓶颈。之前的研究表明,通过持续加热熔化 EVA,可以削弱 EVA 与硅的粘合力。本文展示了一种使用纳秒激光脉冲在 EVA-Si 界面选择性诱导瞬时熔化的新方法。这种脉冲加热方法可以在模型和商用多晶光伏电池板中将玻璃-EVA 层与硅完全分离。这种剥离对激光脉冲能量(单位面积激光脉冲能量)、波长、施加压力和扫描速度等参数的依赖性得到了表征。对于模型光伏板,在重力作用下组件自发分离所需的单脉冲激光能量分别为 0.23、0.32 和 0.78 J/cm2(波长分别为 355 nm、532 nm 和 1064 nm)。使用较短波长可降低脱粘所需的激光通量,而较高的通量可补偿较快的激光束扫描速度。激光照射前后硅表面的光学和电子显微镜图像显示,纹理抗反射层被破坏,但银金属网格保持完好。使用 532 nm 脉冲进行的初步实验表明,激光剥离法可以去除退役商用光伏电池板部分的玻璃-EVA 层,即使顶部玻璃层已出现密集裂纹。
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引用次数: 0
Novel electrochemical process for recycling of valuable metals from spent lithium-ion batteries 从废旧锂离子电池中回收有价金属的新型电化学工艺。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-30 DOI: 10.1016/j.wasman.2024.07.018

Effective recovery of Li, Co, Ni and Mn from cathode materials of spent lithium-ion batteries (LIBs) has become a global concern. In this study, electrolysis of copper sulfate to produce sulfuric acid and electrons were utilized to recover Li, Co, Ni and Mn from spent LIBs. The obtained results showed that 93 % of Ni, 91 % of Co, 89 % of Mn and 94 % of Li were leached and 99 % of Cu was deposited during leaching process by adopting the 0.225 mol/L of copper sulfate with a solid/liquid ratio of 15 g/L at a current density of 50 mA/m2 and 80 °C for 4.5 h. Then, a current efficiency of 72 % for the cathode and 30 % for the anode was achieved at a current density of 40 mA/m2, 70 °C and pH 2.5 during electrodeposition process. The Ni-Co deposition followed the principle of anomalous codeposition and the complete deposition time of Co, Ni and Mn were 3 h, 9 h and 10 h, respectively. Eventually, the Ni, Co, Mn, Li and Cu can be recovered as Ni-Co alloy, MnO2 and Li2CO3 and Cu metals with the corresponding recovery rates of 99.40 %, 91.00 %, 90.68 %, 85.59 % and 89.55 %, respectively. This study proposes a promising strategy for recycling cathode materials from spent LIBs without addition of chemical reductants and acids.

从废锂离子电池(LIB)正极材料中有效回收锂、钴、镍和锰已成为全球关注的问题。本研究利用电解硫酸铜产生硫酸和电子的方法从废锂离子电池中回收锂、钴、镍和锰。结果表明,采用固液比为 15 克/升的 0.225 摩尔/升硫酸铜,在电流密度为 50 毫安/平方米、温度为 80 °C、持续 4.5 小时的浸出过程中,93% 的镍、91% 的钴、89% 的锰和 94% 的锂被浸出,99% 的铜被沉积。镍钴沉积遵循异常共沉积原理,钴、镍和锰的完全沉积时间分别为 3 小时、9 小时和 10 小时。最终,Ni、Co、Mn、Li 和 Cu 可以以 Ni-Co 合金、MnO2 和 Li2CO3 以及 Cu 金属的形式被回收,相应的回收率分别为 99.40%、91.00%、90.68%、85.59% 和 89.55%。这项研究提出了一种无需添加化学还原剂和酸即可从废锂电池中回收阴极材料的可行策略。
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引用次数: 0
Hydrological response and crack resistance of polypropylene-fiber reinforced compacted steel slag-bentonite mixtures under wetting–drying cycles 聚丙烯纤维加固的压实钢渣-膨润土混合物在湿润-干燥循环下的水文响应和抗裂性。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-29 DOI: 10.1016/j.wasman.2024.07.019

Desiccation-induced cracks in a compacted clay liner significantly deteriorate the hydraulic barrier performance of landfill covers. The present study explores the effects of polypropylene (PP) fiber reinforcement on the hydrological response and crack resistance of compacted steel slag (SS; 90 wt%) – bentonite (10 wt%) mixtures under drying and wetting cycles. Comprehensive tests were conducted to explore the impact of different fiber lengths (6–12 mm) and contents (0–0.4 % wt.%), including hydraulic conductivity tests for measuring the saturated hydraulic conductivity (ks), unconfined-penetration tests for measuring the tensile strength, small-sized plate tests for quantifying crack development, and large-sized bucket tests for studying the hydrological response and crack characteristics. Higher fiber contents and longer fiber lengths increased the ks-value of the specimens. For a 0.3 % fiber content, the tensile strength peaked for the 9-mm fiber. Consistently, the specimen reinforced with the 9-mm fibers exhibited significantly fewer cracks than those reinforced with the 6-mm and 12-mm fibers. It was because the 6-mm fibers had a shorter anchorage length, while the 12-mm fibers tended to agglomerate. The large-sized bucket tests showed that fiber reinforcement limited crack development significantly under wetting and drying cycles, reducing the rainfall infiltration by 40 % and enhancing the soil water retention capacity. Finally, a 0.3 wt% of 9-mm PP was recommended to reinforce the compacted SS-bentonite mixtures.

在压实的粘土衬垫中,干燥引起的裂缝会严重影响垃圾填埋场覆盖层的水力阻隔性能。本研究探讨了在干燥和湿润循环条件下,聚丙烯(PP)纤维加固对压实钢渣(SS;90 wt%)-膨润土(10 wt%)混合物的水文响应和抗裂性的影响。为探索不同纤维长度(6-12 毫米)和含量(0-0.4% wt.%)的影响,进行了综合测试,包括测量饱和导水性(ks)的导水性试验、测量抗拉强度的无约束渗透试验、量化裂纹发展的小尺寸板试验以及研究水文响应和裂纹特征的大尺寸桶试验。纤维含量越高、纤维长度越长,试样的 ks 值越高。纤维含量为 0.3% 时,9 毫米纤维的抗拉强度达到峰值。同样,与使用 6 毫米和 12 毫米纤维加固的试样相比,使用 9 毫米纤维加固的试样出现的裂缝要少得多。这是因为 6 毫米纤维的锚固长度较短,而 12 毫米纤维容易聚集。大型水桶测试表明,在潮湿和干燥循环下,纤维加固显著限制了裂缝的发展,将降雨渗透率降低了 40%,并提高了土壤的保水能力。最后,建议使用 0.3 wt% 的 9 毫米聚丙烯来加固压实的 SS-膨润土混合物。
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引用次数: 0
Reuse potential of municipal solid waste incinerator bottom ash as secondary aggregate: Material characteristics, persistent organic pollutant content and effects of pH and selected environmental lixiviants on leaching behaviour 城市固体废物焚化炉底灰作为二次骨料的再利用潜力:材料特性、持久性有机污染物含量以及 pH 值和选定环境活化剂对浸出行为的影响。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-29 DOI: 10.1016/j.wasman.2024.07.026

Increasing municipal solid waste (MSW) production poses challenges for sustainable urban development. Modern energy-from-waste (EfW) facilities incinerate MSW, reducing mass and recovering energy. In the UK, MSW incineration bottom ash (MSW IBA) is primarily reused in civil engineering applications. This study characterizes UK-produced MSW IBA, examining its pH-dependent leaching behaviour and response to environmental lixiviants. Results show predominant components include a melt phase, primary glass and fine ash aggregations, and a chemical composition dominated by SiO2 (30–50 %), CaO (∼15 %), Fe2O3 (∼10 %), and Al2O3 (∼8%). X-ray absorption near edge structure (XANES) analysis shows that Zn and Cu are most likely oxygen-bound (adsorbed to oxy-hydroxides and as oxides) with some sulphur bound. Polychlorinated biphenyls (PCBs) and polychlorinated dibenzodioxins/furans (PCDD/Fs) are well below regulatory limits, and polycyclic aromatic hydrocarbons (PAHs) were undetectable. Leaching tests indicate trace elements mobilize at pHs ≤ 6. With a natural pH of 11.3 and high buffering capacity, significant acid inputs to the MSW IBA are required to reach this pH, which are improbable in the environment. Wood chip additions increase leachate’s dissolved organic carbon (DOC) and reduce pH, but had minimal impact on metal-leaching behaviour. Synthetic plant exudate solutions minimally affect metal leaching at realistic concentrations, only enhancing leaching at ≥ 1500 mg l−1 DOC. This work supports MSW IBA’s low-risk in specified civil engineering applications.

城市固体废弃物(MSW)产量的增加给城市的可持续发展带来了挑战。现代垃圾焚烧发电(EfW)设施可焚烧城市固体废弃物,减少质量并回收能源。在英国,城市固体垃圾焚烧底灰(MSW IBA)主要用于土木工程。本研究描述了英国生产的 MSW IBA 的特征,考察了其随 pH 值变化的浸出行为以及对环境活性剂的反应。结果表明,主要成分包括熔融相、原生玻璃和细灰聚集体,化学成分以二氧化硅(30%-50%)、氧化钙(15%)、氧化铁(10%)和氧化铝(8%)为主。X 射线吸收近缘结构(XANES)分析表明,锌和铜很可能与氧结合(吸附在氧氢氧化物上或作为氧化物),也与一些硫结合。多氯联苯 (PCB) 和多氯二苯并二噁英/呋喃 (PCDD/Fs) 远远低于监管限值,多环芳烃 (PAH) 检测不到。浸出测试表明,微量元素在 pH 值≤ 6 时会发生迁移。由于自然 pH 值为 11.3,且缓冲能力较强,要达到这一 pH 值,需要向 MSW IBA 输入大量酸性物质,而这在环境中是不可能的。添加木屑可增加浸出液的溶解有机碳 (DOC) 并降低 pH 值,但对金属浸出行为的影响微乎其微。合成植物渗出液对实际浓度下的金属沥滤影响很小,只有在 DOC ≥ 1500 毫克/升时才会增强沥滤。这项工作证明了 MSW IBA 在特定土木工程应用中的低风险性。
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引用次数: 0
Pre-separation combined with reduction roasting for high-quality recovery of graphite and lithium from spent lithium ion batteries 预分离与还原焙烧相结合,从废旧锂离子电池中高质量地回收石墨和锂。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-28 DOI: 10.1016/j.wasman.2024.07.030

The recycling of spent lithium ion batteries is of great significance because it contains large amounts of valuable metals. But current recovery methods exhibit limited efficiency in selectively extracting lithium from spent electrode materials and spent graphite becomes metallurgical residues. In this study, we propose a novel recycling flowchart that combines flotation with multi-stage water-leaching to enhance the recovery of graphite and lithium from black mass derived from spent lithium ion batteries. Removal of organics can be conducted by pyrolysis, at the same time, the spent ternary cathode material was decomposed into CoO, NiO, and MnO at a temperature of 600 °C for 60 min using pyrolysis product-derived reductant. The sub-microlevel migration behavior of lithium ions in electrode materials was also examined. The electrode material aggregates were broken up by water crushing, and 38.67 % lithium dissolves into water for recycling. Bubble flotation was used to recycle the excess graphite from the black mass while the residual graphite was used as reductant for the carbothermal reduction. Using the developed scheme, we were able to recover 95.51 % of lithium after carbothermal reduction with 12.31 % carbon residue. Based on basic research, a novel recycling flowchart of spent lithium-ion batteries has been proposed.

废旧锂离子电池含有大量有价金属,因此回收利用意义重大。但目前的回收方法在从废电极材料中选择性提取锂方面效率有限,废石墨也成为冶金残渣。在本研究中,我们提出了一种新颖的回收流程图,将浮选与多级水浸相结合,以提高从废锂离子电池黑液中回收石墨和锂的效率。有机物可通过热解去除,同时,利用热解产物衍生的还原剂,在 600 °C 的温度下将废三元正极材料分解为 CoO、NiO 和 MnO,并持续 60 分钟。此外,还研究了锂离子在电极材料中的亚微米级迁移行为。电极材料聚集体经水破碎后,38.67% 的锂溶解到水中,可回收利用。利用气泡浮选回收了黑块中多余的石墨,而残余石墨则用作碳热还原的还原剂。利用所开发的方案,我们能够在碳热还原后回收 95.51 % 的锂,碳残留量为 12.31 %。在基础研究的基础上,我们提出了一种新型的废锂离子电池回收流程图。
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引用次数: 0
Quantification and forecast of GHG emissions from municipal solid wastes by multi-expression programming method 利用多表达式编程方法量化和预测城市固体废物的温室气体排放量。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-27 DOI: 10.1016/j.wasman.2024.07.027

The municipal solid waste (MSW) management is significantly contributing to global greenhouse gas (GHG) emissions. Analyzing the emission pattern of GHGs from MSW is essential for formulating appropriate carbon mitigation policies. Based on IPCC Models, GHG emissions from MSW were calculated in Chinese provinces from 2004 to 2021 by landfilling and incineration operations, separately. Landfilling and incineration generated approximately 1271 MtCO2-eq and 198 MtCO2-eq from 2004 to 2021, respectively. GHG emissions from landfilling increased from 2004 to 2020 and declined in 2021, while GHG emissions from incineration demonstrated an increasing trend with three distinct growth stages. A panel regression model was then employed to identify the key factors influencing GHG emissions. GDP and population are positively related to GHG emissions from landfills, while PCCE is negatively related to GHG emissions from landfills. GDP and PCCE have a positive impact on GHG emissions from incineration, while population showed no significant impact. Multi-expression programming was used to develop an explicit model, forecasting GHG emissions from MSW by 2030. From 2022 to 2024, GHG emissions from landfills will quickly decrease, while GHG emissions from incineration will rapidly increase. Subsequently, the GHG emission rate of incineration will slow down, and GHGs from landfilling will slowly decrease due to no MSW for landfill disposal. The methods and results provide insightful information for policy-makers and waste management sector.

城市固体废物(MSW)管理对全球温室气体(GHG)排放有重大影响。分析城市固体废物的温室气体排放模式对于制定适当的碳减排政策至关重要。根据 IPCC 模型,分别计算了 2004 年至 2021 年中国各省城市生活垃圾填埋和焚烧产生的温室气体排放量。从 2004 年到 2021 年,填埋和焚烧分别产生了约 1.27 亿吨二氧化碳当量和 1.98 亿吨二氧化碳当量。从 2004 年到 2020 年,填埋产生的温室气体排放量有所增加,到 2021 年则有所减少,而焚烧产生的温室气体排放量则呈上升趋势,并分为三个不同的增长阶段。然后采用面板回归模型来确定影响温室气体排放的关键因素。GDP 和人口与垃圾填埋场的温室气体排放量呈正相关,而 PCCE 与垃圾填埋场的温室气体排放量呈负相关。GDP 和 PCCE 对焚烧产生的温室气体排放有正向影响,而人口则无显著影响。我们使用多重表达式编程建立了一个明确的模型,预测到 2030 年城市固体废物的温室气体排放量。从 2022 年到 2024 年,填埋产生的温室气体排放量将迅速减少,而焚烧产生的温室气体排放量将迅速增加。随后,焚烧的温室气体排放速度将放缓,而填埋产生的温室气体将由于没有城市固体废弃物用于填埋处理而缓慢减少。这些方法和结果为政策制定者和废物管理部门提供了具有洞察力的信息。
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引用次数: 0
Machine learning-aided unveiling the relationship between chemical pretreatment and methane production of lignocellulosic waste 机器学习辅助揭示木质纤维素废物化学预处理与甲烷生产之间的关系。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-27 DOI: 10.1016/j.wasman.2024.07.004

Chemical pretreatment is a common method to enhance the cumulative methane yield (CMY) of lignocellulosic waste (LW) but its effectiveness is subject to various factors, and accurate estimation of methane production of pretreated LW remains a challenge. Here, based on 254 LW samples, a machine learning (ML) model to predict the methane production performance of pretreated feedstock was constructed using two automated ML platforms (tree-based pipeline optimization tool and neural network intelligence). Furthermore, the interactive effects of pretreatment conditions, feedstock properties, and digestion conditions on methane production of pretreated LW were studied through model interpretability analysis. The optimal ML model performed well on the validation set, and the digestion time, pretreatment agent, and lignin content (LC) were found to be key factors affecting the methane production of pretreated LW. If the LC in the raw LW was lower than 15%, the maximum CMY might be achieved using the NaOH, KOH, and alkaline hydrogen peroxide (AHP) with concentrations of 3.8%, 4.4%, and 4.5%, respectively. On the other hand, if LC was higher than 15%, only high concentrations of AHP exceeding 4% could significantly increase methane production. This study provides valuable guidance for optimizing pretreatment process, comparing different chemical pretreatment approaches, and regulating the operation of large-scale biogas plants.

化学预处理是提高木质纤维素废物(LW)累积甲烷产量(CMY)的常用方法,但其效果受各种因素的影响,因此准确估算预处理 LW 的甲烷产量仍是一项挑战。本文以 254 个木质纤维素废料样本为基础,利用两个自动化 ML 平台(基于树的管道优化工具和神经网络智能)构建了一个机器学习(ML)模型,用于预测预处理原料的甲烷生产性能。此外,还通过模型可解释性分析,研究了预处理条件、原料特性和消化条件对预处理 LW 甲烷产量的交互影响。最优 ML 模型在验证集上表现良好,并发现消化时间、预处理剂和木质素含量(LC)是影响预处理 LW 甲烷产量的关键因素。如果原料 LW 中的 LC 低于 15%,则使用 NaOH、KOH 和碱性过氧化氢(AHP)(浓度分别为 3.8%、4.4% 和 4.5%)可获得最大 CMY。另一方面,如果 LC 高于 15%,只有超过 4% 的高浓度 AHP 才能显著提高甲烷产量。这项研究为优化预处理工艺、比较不同的化学预处理方法以及规范大型沼气厂的运行提供了宝贵的指导。
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引用次数: 0
Biochar, phosphate, and magnesium oxide in seaweed and cornstarch dregs co-composting: Enhancing organic matter degradation, humification, and nitrogen retention 海藻和玉米淀粉渣共堆肥中的生物炭、磷酸盐和氧化镁:加强有机物降解、腐殖化和氮的保留。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-25 DOI: 10.1016/j.wasman.2024.07.024

Seaweed waste, abundant and rich in plant-stimulating properties, has the potential to be transformed into valuable soil amendments through proper composting and utilization management. Given its low carbon-to-nitrogen ratio, co-composting seaweed with carbon-rich cornstarch dregs is an effective strategy. However, the potential application of co-composting largely depends on the efficiency of the composting and the quality of the product. This study explores the effects of adding 10 % corn stalk biochar to a co-composting system of seaweed and cornstarch dregs, alongside varying buffering capacities of phosphates (KH2PO4 and K2HPO4·3H2O-KH2PO4) and MgO, on the degradation efficiency of organic matter, nitrogen transformation, and humification. The results indicate that the addition of biochar and salts enhances the oxygen utilization rate (OUR) and cellulase activity during the thermophilic phase. Additionally, X-ray diffraction (XRD) and parallel factor analysis (PARAFAC) demonstrate more intense solubilization and transformation of proteinaceous substances, along with cellulose degradation. These processes are crucial for enhancing organic matter degradation and humification, significantly boosting degradation (with an increase of 28.6 % to 33.8 %) and humification levels (HA/FA increased by 37.1 % to 49.6 %). Specifically, groups with high buffering capacity significantly promote the formation of NO3-N and NH4+-N, and a higher degree of humification, creating an optimal environment for significantly improving nitrogen retention (increased by 4.80 %). Additionally, this treatment retains and slightly enhances the plant-stimulating properties of seaweed. These findings underscore the potential of integrating biochar with specific ratios of phosphates and MgO to enhance composting efficiency and product quality while preserving the plant-stimulating effects of seaweed.

海藻废弃物种类繁多,具有丰富的植物刺激特性,通过适当的堆肥和利用管理,有可能转化为有价值的土壤改良剂。鉴于海藻的碳氮比较低,将海藻与富含碳的玉米淀粉渣共同堆肥是一种有效的策略。然而,共堆肥的潜在应用在很大程度上取决于堆肥的效率和产品的质量。本研究探讨了在海藻和玉米淀粉渣的共堆肥系统中添加 10% 的玉米秸秆生物炭以及不同缓冲能力的磷酸盐(KH2PO4 和 K2HPO4-3H2O-KH2PO4)和氧化镁对有机物降解效率、氮转化和腐殖化的影响。结果表明,在嗜热阶段,添加生物炭和盐类可提高氧利用率(OUR)和纤维素酶活性。此外,X 射线衍射(XRD)和平行因子分析(PARAFAC)表明,蛋白质物质的溶解和转化以及纤维素降解更为强烈。这些过程对提高有机物降解和腐殖化至关重要,可显著提高降解率(从 28.6% 提高到 33.8%)和腐殖化水平(HA/FA 从 37.1% 提高到 49.6%)。具体来说,缓冲能力强的组群可显著促进 NO3-N 和 NH4+-N 的形成,并提高腐殖化程度,从而为显著提高氮保留率(提高 4.80%)创造最佳环境。此外,这种处理方法还保留并略微增强了海藻的植物刺激特性。这些发现强调了将生物炭与特定比例的磷酸盐和氧化镁结合起来,在保留海藻的植物刺激作用的同时提高堆肥效率和产品质量的潜力。
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引用次数: 0
Removal of the heavy metals from copper slag by using carbonless additives 使用无碳添加剂去除铜渣中的重金属。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-25 DOI: 10.1016/j.wasman.2024.07.023

The smelting processes account for over 80 % of global copper production, generating various slags in large quantities. Most of these slags do not contain the required amounts of valuable metals to justify economic revalorization, yet the concentrations present may negatively affect the environment. In this study, heavy and potentially toxic metals were removed by keeping the liquefied slag at 1300 °C for four hours, while the metals gathering was enhanced by adding silicon-copper compounds. Crystallography, metallography, gravimetric, thermogravimetric, and differential thermal analysis were employed to characterize the slag. Electron probe microanalysis was utilized to examine the distribution of heavy and potentially toxic metals from the original copper slag to the remaining slag and mattes formed in the lower portion of the containing vessel. In all instances, concentrations of the arsenic and zinc were reduced below the detection limit. Moreover, the cumulative concentrations of six heavy metals were reduced from 2400 ppm in the initial slag to 41.7 ppm in the remaining slag when using 30 wt%Si70wt%Cu additive. All potentially valuable or toxic metals gathered in the mattes that had oxygen concentrations about 50 times lower than in the initial slag, at 0.82, 0.56, and 0.68 wt% after the mixing slag with 10 wt%Si90%Cu, 30 wt%Si70wt%Cu, and 50 wt%Si50wt%Cu additives, respectively. Investigated practices can mitigate the threat of heavy and potentially toxic metals associated with the disposal of copper slags while also enabling the recovery of valuable metals and rendering the remaining slag suitable for construction or mine backfill purposes.

冶炼过程占全球铜产量的 80% 以上,会产生大量各种废渣。这些炉渣中的大部分都不含所需数量的有价金属,因此无法进行经济上的重新评估,但其浓度可能会对环境造成负面影响。在这项研究中,通过将液化炉渣在 1300 °C 下保持四小时,去除了重金属和潜在有毒金属,同时通过添加硅铜化合物提高了金属聚集能力。该研究采用了晶体学、金相学、重量分析、热重分析和差热分析等方法对炉渣进行表征。电子探针显微分析法用于检查重金属和潜在有毒金属从原始铜渣到剩余铜渣的分布情况,以及在容器下部形成的哑光。在所有情况下,砷和锌的浓度都降至检测限以下。此外,当使用 30 wt%Si70wt%Cu 添加剂时,六种重金属的累积浓度从最初铜渣中的 2400 ppm 降至剩余铜渣中的 41.7 ppm。在使用 10 wt%Si90%Cu、30 wt%Si70wt%Cu 和 50 wt%Si50wt%Cu 添加剂混合熔渣后,所有可能有价值或有毒的金属都聚集在氧浓度比初始熔渣低约 50 倍的锍中,分别为 0.82、0.56 和 0.68 wt%。所研究的方法可以减轻与铜渣处置相关的重金属和潜在有毒金属的威胁,同时还能回收有价值的金属,并使剩余的铜渣适用于建筑或矿山回填用途。
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引用次数: 0
Organic acid-mediated leaching kinetics study and selective extraction of Mo, V, and Ni from spent catalysts 有机酸介导的浸出动力学研究以及从废催化剂中选择性提取钼、钒和镍。
IF 7.1 2区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-07-24 DOI: 10.1016/j.wasman.2024.07.022

This article employs six organic acids to selectively dissolve Mo, Ni and V from spent catalysts, and the most effective acid is identified. Then, the effects of key leaching parameters, including acid concentration, temperature, and S/L ratio, on metal leaching are systematically explored to determine the leaching mechanism. The results demonstrate that the leaching ability of organic acids followed the order: oxalic acid > citric acid > tartaric acid > malonic acid > acetic acid > formic acid. The leaching process of metals was jointly influenced by acidolysis and complexolysis. Among them, more than 93.07 % of Mo, 86.64 % of V, and 74.21 % of Ni were selectively leached with oxalic acid at the optimum condition: S/l: 1/20, oxalic acid: 1.0 mol/L, temp: 60 °C. From the correlation coefficients, the resulting activation energies, and n values, it was demonstrated that Mo and V followed the Avrami dissolution reaction model, V leaching was controlled by the diffusion mode, and Mo leaching was controlled by a mixed mode of chemical reaction and diffusion. The dissolution behavior of both metals consistently adhered to the linear trend of the Avrami kinetic model under varying S/L ratios and oxalic acid concentrations.

本文采用六种有机酸选择性地溶解废催化剂中的钼、镍和钒,并确定了最有效的酸。然后,系统地探讨了酸浓度、温度和 S/L 比等关键浸出参数对金属浸出的影响,以确定浸出机理。结果表明,有机酸的浸出能力依次为:草酸 > 柠檬酸 > 酒石酸 > 丙二酸 > 乙酸 > 甲酸。金属的浸出过程受到酸解和络解的共同影响。其中,在最佳条件下,超过 93.07% 的 Mo、86.64% 的 V 和 74.21% 的 Ni 被草酸选择性浸出:S/L:1/20,草酸:1.0 mol/L,温度:60 °C。从相关系数、产生的活化能和 n 值可以看出,钼和钒遵循阿夫拉米溶解反应模型,钒的浸出受扩散模式控制,而钼的浸出受化学反应和扩散混合模式控制。在不同的 S/L 比率和草酸浓度下,两种金属的溶解行为始终遵循阿夫拉米动力学模型的线性趋势。
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引用次数: 0
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Waste management
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