炼铜炉渣的显微分析与渣含铜

采用光学显微镜和扫描电镜，研究了空气熔炼和富氧熔炼条件下炼铜炉渣试样的显微结构。在低倍的条件下测定了渣中含铜物相的粒级分布及其与周围物相种类的关系，用元素面扫描的方法逐一鉴定了渣中各物相的形态与组成；用微区分析的方法确定了不同粒径含铜物相化学成分的差异，发现含铜物相的粒径越大，其含铜越高。分析中注意到不同氧化程度的渣中磁铁矿相结晶形态和数量的不同，氧化越甚，磁铁矿晶体发育越完全，渣含铜就越高。     

还原熔炼法从谦比希铜冶炼厂转炉渣中回收钴(英文)

研究从赞比亚谦比希铜冶炼厂转炉渣中回收钴的还原熔炼过程。实验考察还原剂用量、熔炼温度、保温时间及渣型改善剂CaO和TiO2的添加对还原熔炼金属回收率的影响。采用X射线衍射、扫描电子显微镜及能谱分析对所得贫化渣和含钴合金进行表征。结果表明,在优化条件下,转炉渣中钴、铜、铁的回收率分别为94.02%,95.76%和小于18%;贫化渣的主要物相组成为铁橄榄石和铁尖晶石,含钴合金中主要含有金属铜、含钴铜的铁合金和少量的硫化物。     

含砷石灰铁盐渣的理化特性及其浸出行为（英文）

以典型石灰铁盐法处理二种含砷废水产生的污泥(污酸渣和砷酸钙渣)为研究对象,采用ICP-AES、SEM-EDS、XRD、XPS和化学物相分析等检测手段对其化学组成、形貌特征、物相结构及砷的赋存状态进行研究,采用毒性浸出实验和BCR三步连续提取法考察污泥中砷的浸出行为。研究结果表明,污酸渣和砷酸钙渣中砷的含量分别为2.5%和21.2%,主要组成物相为砷酸盐及砷氧化物,均以无定型的颗粒均匀分散或团聚在污泥中。砷的浸出毒性超出TCLP标准规定限值的119和1063倍,浸出率分别为47.66%和50.15%。砷以酸可提取态和可还原态为主,两者共占90%左右,而稳定的残渣态含量相对较低,这是含砷石灰铁盐渣浸出毒性大、环境活性高的直接原因。本研究为含砷石灰铁盐渣无害化处理技术提供了大量有用的基本数据。     

湿法炼锌铜砷渣分离提铜及沉砷工艺研究

采用铁粉置换法处理湿法炼锌产生的锌浸渣还原浸出液,产出一种含砷铜渣,以该含砷铜渣为研究对象,利用氧压酸浸缓慢分解含砷铜渣,使其中的铜、锌等溶解进入溶液,同时,砷、铁以臭葱石的形式沉淀为浸出渣,从而将铜的浸出和砷、铁的沉淀在同一反应釜同一过程中完成,有效实现含砷铜渣中有价金属的浸出过程与杂质的沉淀过程在同一过程同步进行。结果表明：在反应温度为135℃、反应时间为4 h、液固体积质量比25 mL/g、硫酸浓度为50 g/L、氧分压500 kPa、铁砷摩尔比为1的条件下,浸出渣中铜含量仅为2.03%,浸出率达到97.72%,砷含量达到26.06%,沉淀率达到95.98%;浸出液中铜的浓度达到20.47 g/L,砷浓度小于0.63 g/L,实现了铜和砷的高效分离,提高了铜金属回收率和资源综合利用率。浸出渣中砷均以臭葱石(FeAsO₄·2H₂O)的形式存在,符合当前的环境友好型发展理念。     

铜冶炼烟尘与污酸协同浸出体系中铜砷浸出行为

铜冶炼过程产生的烟尘和污酸等危险废物的无害化处理及有价金属的综合高效回收是铜冶炼行业亟待解决的重大环保问题.本研究采用"以废制废"的研究思路,利用污酸中的游离酸实现铜冶炼烟尘中有价金属的高效浸出.开展了铜冶炼烟尘与污酸协同浸出实验,深入研究关键宏观技术参数对铜、砷浸出率以及复杂砷物相的溶解及沉淀过程矿相转变行为的影响规...     

无定形FeS的缓释效应及其在铜砷硫化分离中的应用

铜烟灰中砷与有价金属的高效分离一直是制约二次资源利用的核心问题。以典型铜冶炼烟灰为原料,研究了影响烟灰选择性湿法脱砷的主要因素以及无定形FeS代替传统硫化剂在烟灰浸出液中的铜砷高效硫化分离行为。结果表明：在最佳浸出条件下,烟灰中铜浸出率超过95%,砷浸出率超过86%;无定形FeS随着陈化时间的延长,由无定形逐渐趋于晶体化,反应活性逐渐减弱;与Na₂S相比,无定形FeS具有良好的硫源缓释效应可有效减少反应过程中H₂S气体的逸出和改善产物的结晶性能。无定形FeS在实际浸出液中对铜的去除率大于99%,硫化铜渣中砷含量不超过2%(质量分数);缓释除砷阶段渣砷品位大于25%。无定形FeS为铜烟灰中有价金属与砷的分离提供了一种较优的备选方案。     

奥斯麦特炉熔炼中渣含铜问题的探讨

分析了奥斯麦特熔炼炉渣的含铜形态和损失途径,提出了降低渣含铜的几点建议及应采取的措施,以达提高金属回收率,获取较好的经济效益和社会效益之目的。     

脆硫铅锑精矿富氧直接熔炼渣型理论研究

对脆硫铅锑精矿富氧直接熔炼渣型理论进行研究。根据富氧直接熔炼过程炉渣组成特性,选取FeO-SiO_2-CaO-ZnO渣系为研究对象。采用热力学软件Factsage计算并绘制FeO-SiO_2-CaO-ZnO渣系相图,考察CaO与SiO_2质量比、Fe与SiO_2质量比、ZnO含量及温度对该渣系熔化温度及黏度的作用规律,并在此理论基础上进行实验研究。理论研究表明,熔炼过程炉渣中Fe与SiO_2质量比和CaO与SiO_2质量比的增大均会提高炉渣的熔化温度。随着体系温度的升高,炉渣的黏度逐渐减小,1250℃时,炉渣的黏度均小于0.5 Pa·s。实验结果表明:熔炼过程产出合金品位为95.56%,合金直收率达到58.47%,渣中金属含量(Pb与Sb)小于1%(质量分数)。熔炼产物工艺矿物学研究发现,合金中主要物相为金属Pb、金属Sb以及少量Cu_2Sb、FeSb_2金属间化合物,炉渣主要由钙铁橄榄石、铁橄榄石组成,原料中锌主要以氧化锌形式进入渣相。     

不同喷吹气体对铜冶炼熔渣中砷气化脱除的影响（英文）

为了减少铜熔炼渣中砷所带来的环境问题，提出一种基于气体喷吹脱除熔融铜渣中砷的方法，期望在铜回收工艺前将铜熔炼渣中的砷尽可能以粉尘的形式富集。对比惰性气体、氧化性气体和还原性气体对熔渣中砷脱除的影响。氧化性气体CO₂氧化夹杂冰铜中的砷及砷硫化物，并充当气体载体将砷氧化物带出熔池。还原性气体CO可以将FeO_x-SiO₂熔渣中的砷氧化物还原，并使其挥发至气相，可以实现60%以上的砷脱除率。该研究为熔炼渣中砷脱除提供指导。     

铜/铅锌冶炼厂硫化砷渣的理化与环境特性（英文）

以铜冶炼和铅锌冶炼产生的硫化砷渣为研究对象,采用XRD、Raman、SEM-EDD、TG-DTA、XPS和化学物相分析等检测手段研究其理化特性。采用毒性浸出程序(TCLP)、毒性浸出测试国家标准(CSLT)、三步连续浸提程序(BCR)和批次浸出实验(BLE)分析硫化砷渣的环境稳定性。不同冶炼厂的硫化砷渣理化和环境特性具有明显的差异。物相组成和显微分析表明,ASS-I主要由超细的絮状颗粒组成,这种颗粒为粘附有无定型硫的无定型硫化砷。AAS-II主要组成为无定型硫化砷。两种来源的硫化砷渣中砷均为正三价,但是硫的价态组成则有所不同。同时,两种来源的硫化砷渣均具有热不稳定性。TCLP和CSLT结果表明,浸出液中砷和铅的浸出浓度超过了标准限值。超过5%和90%的砷以酸可溶态和可氧化态赋存,这解释了硫化砷渣砷浸出毒性高、环境活性强的原因。本研究为铜和铅锌冶炼企业的硫化砷渣的处置提供了全面的信息参考。     

Assessment of selective sequential extraction procedure for determining arsenic partitioning in copper slag

An optimized selective sequential extraction (SSE) procedure was developed to assess the arsenic (As) partitioning in copper slag. The potential As species in copper slag are partitioned into the readily soluble As, dissolvable arsenates, sparingly soluble arsenates, As residing in sulfides, arsenopyrite and metal As, as well as As incorporated into glassy silicates. The inductively coupled plasma atomic emission spectrometry (ICP-AES), scanning electronic microscopy (SEM), transmission electron microscope (TEM), X-ray diffractometry (XRD) and Fourier transform infrared spectroscopy (FTIR) were used to characterize the leachates and residues produced from the operation scheme. The selectivity and recovery of extractants were evaluated through single-phase extraction procedures. Partitioning data of As in slag samples show good agreement with the reported works and the total As recovery of each operation is over 90%. This suggests that the optimized SEE scheme can be reliably employed for As partitioning in As-bearing byproducts from copper smelting.     

铜复杂资源熔炼过程中杂质锑脱除的热力学模拟（英文）

研究铜冶炼过程Sb的反应机理,分析Sb在4种典型铜冶炼工艺中多相分配差异。建立富氧底吹铜冶炼工艺的多相平衡模型,研究原料中Cu、S和Sb含量对Sb多相分配比的影响。同时,应用该模型研究铜锍品位、富氧浓度、熔炼温度和氧矿比(标准状态下氧气流量与精矿加料速率之比)等工艺参数对Sb分配行为的影响。结果 表明,计算数据与实际生产结果和文献数据吻合良好。提高精矿中Cu含量、降低S和Sb含量,提高铜锍品位、富氧浓度和氧矿比,同时适当降低冶炼温度,有利于Sb向炉渣中定向富集。模拟结果可为复杂资源清洁高效处理及伴生元素综合回收提供理论指导。     

Recovery of valuable metals from spent lithium ion batteries by smelting reduction process based on FeO–SiO2–Al2O3 slag system

A novel smelting reduction process based on FeO–SiO₂–Al₂O₃ slag system for spent lithium ion batteries with Al cans was developed, while using copper slag as the only slag former. The feasibility of the process and the mechanism of copper loss in slag were investigated. 98.83% Co, 98.39% Ni and 93.57% Cu were recovered under the optimum conditions of slag former/battery mass ratio of 4.0:1, smelting temperature of 1723 K, and smelting mass ratio of time of 30 min. The FeO–SiO₂–Al₂O₃ slag system for the smelting process is appropriate under the conditions of m(FeO):m(SiO₂)=0.58:1–1.03:1, and 17.19%–21.52% Al₂O₃ content. The obtained alloy was mainly composed of Fe–Co–Cu–Ni solid solution including small amounts of matte. The obtained slag mainly consisted of fayalite and hercynite. Meanwhile, the mechanism of copper loss is the mechanical entrainment from strip-like fayalite particles in the main form of copper sulfide and metallic copper.     

EFFECTS OF TEMPERATURE ON DISTRIBUTION BEHAVIORS OF MINOR ELEMENTS IN COPPER FLASH SMELTING──COMPUTER SIMULATION

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涡流贫化法回收铜渣中的金、银、铜

采用熔融铜渣为原料,经过涡流贫化过程,回收铜渣中的金、银、铜,贫化渣进一步升温还原得到含铜铁水,最终可制备成耐磨铸铁。结果表明,通过涡流贫化,铜渣中的Fe_3O_4被还原为FeO,然后FeO与SiO_2结合,生成Fe_2SiO_4。经过涡流贫化后,金、银、铜的回收率分别达到了99.44%、93.97%和93.14%。贫化渣中Fe_3O_4和铜的含量分别为1.53%和0.61%(质量分数)。贫化渣涡流还原后得到的含铜铁水制备的耐磨铸铁成分满足高铬耐磨铸铁国标要求。     

Minimization of Copper Losses in Copper Smelting Slag During Electric Furnace Treatment

In the quest to achieve the highest metal recovery during the smelting of copper concentrates, this study has evaluated the minimum level of soluble copper in iron-silicate slags. The experimental work was performed under slag-cleaning conditions for different levels of Fe in the matte and for a range of Fe/SiO₂ ratios in the slag. All experiments were carried out under conditions where three phases were present (copper?Cmatte?Cslag), which is the condition typically prevailing in many slag-cleaning electric furnaces. The %Fe in the electric furnace matte was varied between 0.5?wt.% and 11?wt.%, and two different Fe/SiO₂ ratios in the slag were used (targeted values were 1.4 and 1.6). All experiments were performed at 1200°C. From thermodynamic considerations, from industrial experience, and from the results obtained in this study, the minimum soluble copper content in the electric furnace slag is expected to be near 0.55?wt.% Cu. This level does not account for a portion of the copper present as mechanically entrained matte/metal droplets. Taking this into account, the current authors believe an overall copper level in discard slag between 0.7?wt.% and 0.8?wt.% can be obtained with optimal operating conditions. For these conditions, the copper losses in the slag are roughly 75% as dissolved copper and 25% as entrained matte and copper. Such conditions include operating the electric furnace at metallic copper saturation, maintaining the %Fe in the electric furnace matte between 6?wt.% and 9?wt.%, not exceeding a slag temperature of 1250°C, and controlling the Fe/SiO₂ ratio in the smelting furnace slag at ??1.5. In addition, magnetite reduction needs to be performed efficiently during the slag-cleaning cycle so as to maintain a total magnetite content of ??7?wt.% in the discard slag. The authors further consider that under exceptionally well-controlled conditions, a copper content in electric furnace discard slag between 0.55?wt.% and 0.7?wt.% can be obtained, by minimizing entrained matte and copper solubility in the discard slag.     

含铜砷的铜电解黑泥氧化酸浸-硫化沉淀分离和回收铜

开发从含铜砷的铜电解黑泥中分离和回收铜的湿法冶金新工艺.该工艺包括黑泥氧化酸浸和浸出液中选择性硫化沉铜两个步骤.研究各种工艺参数对铜和砷的浸出和沉淀的影响.在第一阶段中,最佳工艺条件为:初始H2SO4浓度为1.0 mol/L,液固比为10 mL/g,80℃下连续浸出4 h.此条件下铜浸出率可达95.2％,砷浸出率为97...     

基于数值模拟的闪速连续炼铜炉型结构研究

分析4种闪速连续炼铜炉型的本质特性,提出将闪速连续炼铜过程视为由相对独立的闪速造锍熔炼过程和连续吹炼造铜过程构成,分别建立闪速造锍熔炼多相平衡数学模型和连续吹炼造铜局域平衡数学模型,并通过中间物料的传递将两模型有机结合,从而构建完整的闪速连续炼铜过程热力学模型。运用此模型,考察炉型结构对闪速连续炼铜过程的粗铜生成条件、Fe3O4行为、铜在渣中损失以及铜直收率等因素的影响。结果表明：相对于其他3种炉型,甩渣吹炼双烟道D型炉是比较理想的连续炼铜炉体;对于闪速连续炼铜,造锍熔炼段和铜锍吹炼段宜在相对独立的分区进行,各自炉渣和烟气也应分开排出炉体。     

Oxidation leaching of copper smelting dust by controlling potential

A study was conducted for metal extraction from copper smelting dust using the oxidation leaching and control of potential technology. The effects of H₂O₂ dosage, H₂O₂ feeding speed, initial HCl concentration, leaching temperature, liquid-to-solid ratio and leaching time on metals leaching efficiencies were investigated. The following optimized leaching conditions were obtained: H₂O₂ dosage of 0.8 mL/g (redox potential of 429 mV), H₂O₂ feeding speed of 1.0 mL/min, initial H₂SO₄ concentration of 1.0 mol/L, initial HCl concentration of 1.0 mol/L, leaching temperature of 80 °C, initial liquid-to-solid ratio of 5:1 mL/g and leaching time of 1.5 h. Under the optimized conditions, copper and arsenic can be effectively leached from copper smelting dust, leaving residue as a suitable lead resource. The average leaching efficiencies of copper, arsenic and iron are 95.27%, 96.82% and 46.65%, respectively.