Physicochemical and environmental properties of arsenic sulfide sludge from copper and lead−zinc smelter

Physicochemical properties of arsenic sulfide sludge (ASS) from copper smelter (ASS-I) and lead−zinc smelter (ASS-II) were examined by XRD, Raman spectroscopy, SEM−EDS, TG−DTA, XPS and chemical phase analysis method. The toxicity characteristic leaching procedure (TCLP), Chinese standard leaching tests (CSLT), three-stage sequential extraction procedure (BCR) and batch leaching experiments (BLE) were used to investigate the environmental stability. The ASSs from different smelters had obviously different physicochemical and environmental properties. The phase composition and micrograph analysis indicate that ASS-I mainly consists of super refined flocculent particles including amorphous arsenic sulfide adhered with amorphous sulfur and that ASS-II mainly consists of amorphous arsenic sulfide. The valence state of arsenic in both sludges is trivalent, but the valence composition of sulfur is quite different. The ASSs have thermal instability properties. The results of TCLP and CSLT indicate that the concentrations of As and Pd in the leaching solution exceed the standard limits. More than 5% and 90% of arsenic are in the form of acid soluble and oxidizable fractions, respectively, which explains the high arsenic leaching toxicity and environmental activity of ASS. This research provides comprehensive information for the disposal of ASS from copper and lead−zinc smelter.     

铂钯精矿湿法分离Bi、Fe富集贵金属工艺

以铜阳极泥分铜液还原所得铂钯精矿为原料,根据其矿物特性选择HCl作为浸出剂湿法脱除Bi、Fe等主要贱金属元素,富集Au、Ag、Pt、Pd等贵金属;通过热力学计算绘制Bi(Ⅲ)、Fe(Ⅲ)在盐酸体系的组分分布图,实验考察了HCl浓度、Cl-浓度、反应温度和时间等因素对Bi、Fe浸出率的影响.结果表明:在HCl浓度为2 m...     

Physicochemical properties of arsenic-bearing lime–ferrate sludge and its leaching behaviors

Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime–ferrate sludges (ABLFS), waste acid residue (WAR) and calcium arsenate residue (CAR), are comprehensively described. The chemical composition, morphological features, phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP–AES, SEM–EDS, XRD, XPS and chemical phase analysis. The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors. The results show that the contents of arsenic in WAR and CAR are 2.5% and 21.2% and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles. The leaching concentrations of arsenic excess 119 and 1063 times of TCLP standard regulatory level with leaching rates of 47.66% and 50.15% for WAR and CAR, respectively. About 90% of extracted arsenic is in the form of acid soluble and reducible, which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS. This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime–ferrate process.     

某氰化渣的改性石硫合剂法浸金研究

某氰化渣中金的品位为12.03 g/t,氰化渣里游离金的颗粒极细,并且被铁氧化物包裹,难以解离,属于难浸类金矿。采用改性石硫合剂对氰化渣进行了浸金研究,考察了超细磨时间、氧化剂用量、矿浆p H和搅拌时间对金浸出率的影响。优化实验条件为:超细磨时间2 h、氧化剂Ca O2用量0.78 g/500 g、矿浆p H≈11.5、液固比2:1、搅拌浸出时间24 h,金的浸出率达78.57%。     

砷碱渣稳定化处理合成臭葱石晶体固砷

砷碱渣中含有剧毒可溶性砷化合物,若不妥善处置,易造成水体污染和生物中毒。本研究目的是将砷碱渣中的砷转化为大颗粒晶型臭葱石以利于安全储存。在制备臭葱石晶体的反应中,考察了初始pH值、Fe/As摩尔比和反应温度对沉砷率及臭葱石形成的影响,并探究了不同条件下得到的沉淀的浸出毒性。结果表明:当初始pH值为1.0～2.0、Fe/As摩尔比为0.5～3.0及反应温度为105～175℃时,沉砷率可达80%以上,所得臭葱石晶体的As浸出浓度低于5 mg/L。在初始pH值为1.5、Fe/As摩尔比为1.0及反应温度为150℃的优化条件下,得到的臭葱石晶体呈八面体形状,颗粒尺寸可达20μm,且As浸出浓度低至0.08 mg/L,适于稳定化处理砷并长期安全储存。     

氧化锌贫矿提锌渣中铅和银的氯盐一步浸出

运用X射线衍射、扫描电镜和X射线能谱等分析手段,对山东某地深度氧化锌贫矿提锌后渣进行工艺矿物学特征分析可知,矿物中金属赋存状态复杂,属难选矿物。开发出氯盐一步法浸出铅和银的新工艺,考察反应温度、NaCl浓度、添加剂用量、液固比、HCl加入量和浸出时间对浸出过程的影响。结果表明:加入添加剂对铅的浸出率没有影响,但可以显著提高银的浸出率。条件试验研究得出最佳工艺条件如下:浸出温度90℃、NaCl浓度390 g/L、添加剂用量15 mL、液固比(质量比)7?1、HCl加入量3 mL、浸出时间3 h。在此最佳工艺条件下,铅的浸出率达到95%左右,银的浸出率达到90%左右。     

钢铁厂烧结机头灰中铅的配位浸出行为与综合回收

针对钢铁厂烧结机头灰中富含铅、铁、碳、钾、氯等多种有价元素的特点,根据氯离子与铅配位的特性,采用配位浸出的方式实现铅与铁、碳等元素的选择性分离回收。SEM-EDS、XRD等研究分析表明,烧结机头灰中铅主要以絮状的KPb₂Cl₅等物相吸附于铁氧化合物、硅铝酸盐和碳颗粒表面,铁主要以Fe₂O₃和Fe₃O₄物相存在。实验考察了溶液pH值、温度、氯离子浓度、浸出时间和液固比等因素对铅浸出率的影响。研究表明,在溶液pH值为3.0,浸出温度为80℃,氯离子浓度为6 mol/L,液固比(mL/g)为10:1,浸出时间为2 h的优化条件下,烧结机头灰中铅化合物与氯发生配位溶解反应生成PbCl_i^2-i(i=1～4)等易溶解的络合离子,实现铅的浸出,铅浸出率为95.7%;而烧结机头灰中对钢铁冶炼有用的铁、碳、硅、铝等元素不被浸出,富集在浸出渣中,较好地实现了选择性浸出。浸出液中的铅经冷却结晶、洗涤纯化后,获得纯度为99%的氯化铅产品...     

Recovery of valuable metals from zinc leaching residue by sulfate roasting and water leaching

Zinc leaching residue (ZLR), produced from traditional zinc hydrometallurgy process, is not only a hazardous waste but also a potential valuable solid. The combination of sulfate roasting and water leaching was employed to recover the valuable metals from ZLR. The ZLR was initially roasted with ferric sulfate at 640 °C for 1 h with ferric sulfate/zinc ferrite mole ratio of 1.2. In this process, the valuable metals were efficiently transformed into water soluble sulfate, while iron remains as ferric oxide. Thereafter, water leaching was conducted to extract the valuable metals sulfate for recovery. The recovery rates of zinc, manganese, copper, cadmium and iron were 92.4%, 93.3%, 99.3%, 91.4% and 1.1%, respectively. A leaching toxicity test for ZLR was performed after water leaching. The results indicated that the final residue was effectively detoxified and all of the heavy metal leaching concentrations were under the allowable limit.     

柿竹园铅锌尾矿湿化学法合成硅酸钙粉末

将柿竹园铅锌矿破碎球磨,进行煅烧、除硫,经浓盐酸酸洗、过滤,实现了有价元素与其他元素的分离,通过控制不同的pH值,分别得到铁和铅锌的氢氧化物,再往滤液中加入NH4HCO3,钙以CaCO3的形式沉淀出来,将所得的碳酸钙经硝酸溶解后,加入适量的硅酸钠,并用聚乙二醇作为分散剂,制得硅酸钙粉体.并对制各的溶液和滤渣进行了表征,研究了焙烧物料的数量和金属的离子价态对产物纯度和回收率的影响.本试验通过控制适宜的工艺条件,使铁和钙的浸出率分别达到83.2%和67.7%,工艺简便,成本较低,实现了矿产资源的综合利用.     

Process for Complete Utilization of Zinc Leach Residues

Filter residues are mixed in high proportion with pyrite cinders and subjected to a modified chloridizing and sulfatizing roast in standard multiple-hearth furnaces. By additions of sodium chloride and of suitable sulfur-bearing materials, the metals Cu, Zn, and Cd, as well as Ag and Au, are rendered soluble to a large extent. By leaching with acid, Zn, Cu, Ag, Cd, and Au are eluted. The remaining iron oxide is conveyed into sintering or pelletizing plants.If the residues contain in addition undesirable elements such as As, Sb, and Sn, they are first subjected to a chloridizing and sulfatizing roast; Cu, Zn, and the noble metals are extracted by leaching. The fine-grained iron oxide, containing As, Sb, and Sn, is either discarded or purified from these elements by means of chloridizing volatilization in a reducing atmosphere. Given sufficiently high contents, these accompanying elements can be recovered economically.In recovering the nonferrous metals from the solutions, the classical precipitation and cementation processes, well tried under plant conditions, are compared with ion exchange processes with regard to cost and process efficiency. Pilot plant results of the application of ion exchangers to solutions of higher concentration are given.     

Recovery of Precious and Base Metals from Waste Printed Circuit Boards Using a Sequential Leaching Procedure

This paper considers the issue of recycling of waste printed circuit boards (WPCBs) containing precious and base metals in appreciable amounts. High-pressure oxidative leaching (HPOL) with dilute sulfuric acid resulted in removal of a significant amount of base metals from a WPCB ash sample obtained by incineration at 800°C. The parameters investigated in the precious metal leaching from WPCB residue after HPOL included the sulfuric acid concentration, thiourea concentration, oxidant concentration, leaching temperature, and leaching time. Recovery of gold, silver, and palladium of 100%, 81%, and 13% from the WPCB residue sample was achieved by thiourea leaching under optimized conditions. The results show that the efficiency of precious metal dissolution from the WPCB sample using thiourea solution depended strongly on the concentration of both thiourea and oxidant.     

Preparation of pure SbCl3 from lead anode slime bearing high antimony and low silver

A novel treatment process of lead anode slime bearing high antimony and low silver was developed by a potential-controlled chloridization leaching and continuous distillation.The experimental results show a high Sb 3+ concentration,489.2 g/L,in the leaching solution for two-stage countercurrent leaching process,and the leaching rates of Sb,Cu,Bi more than 99% when the potential is controlled at 450 mV.When the leaching solution is distillated and concentrated at 120°C,almost all the silicon compound is evaporated into the concentration distillate and exists as amorphous hydrated silica.By the continuous distillation,high pure SbCl3 could be prepared,and AsCl3 is enriched in the distillate while metals Bi,Cu are enriched in the continuous distillation residue.As a result,the recovery rate of Sb is more than 95%.     

磁化焙烧对氰化尾渣中金、铁回收的影响(英文)EI北大核心CSCD

对氰化尾渣的焙烧预处理及其对有价金属综合回收的影响进行了研究。结果表明:当焙烧温度为750℃、焙烧时间为1.25h、还原剂添加量为6%时,铁的磁化率为86.27%,金的浸出率达到46.14%。结合矿物构造与赤铁矿磁化焙烧原理,探讨了焙烧对金浸出影响的机理,认为赤铁矿磁化焙烧后解离出的包裹金,是提高金浸出率的主要来源。     

Technological mineralogy and environmental activity of zinc leaching residue from zinc hydrometallurgical process

Chemical, physical, structural and morphological properties of zinc leaching residue were examined by the combination of various detection means such as AAS, XRF, XRD, Mössbauer spectrometry, SEM-EDS, TG-DSC, XPS and FTIR. The toxicity characteristic leaching procedure (TCLP) was used to investigate the environmental activity of zinc leaching residue for a short contact time. The phase composition analysis indicated that the zinc leaching residue mainly consists of super refined flocculent particles including zinc ferrite, sulfate and silicate. The physical structural analysis showed that it has a thermal instability and strong water absorption properties. The results of TCLP indicated that the amounts of Zn and Cd in the leaching solution exceed 40 and 90 times of limit, respectively, which demonstrate that this residue is unstable in weak acidic environment for a short contact time.     

从锌浸出渣中回收银的方法

一般湿法炼锌厂所产出的锌浸出渣含有相当数量的银、锌及稀散金属。近２０年来，人们从这类残渣中回收银及人价金属的研究和生产方法归纳起来可分为３类；浮选富集，火法富集和直接浸出银。讨论了各种方法的基本原理，优点和缺点，以及研究方向。     

从热滤渣中富集提取贵金属

介绍了减压蒸馏脱硫，熔炼富集，高温悬浮氯气浸出处理热滤渣的工艺。其综合利用好，元素硫脱除率〉９２％，贱金属浸出率〉９５％，贵金属回收率〉９９％。贵金属富集物可并入贵金属精炼分离工段处理。     

回转窑内渣成分优化实现锌铅元素的高效回收（英文）

在回转窑内从高硅锌浸出渣中实现高效回收锌铅金属。XRD、SEM、EDS及ICP表征结果表明,浸出渣含12.4%SiO₂、16.1%Zn和7.4%Pb(质量分数)。热力学分析表明,在回转窑内1150～1250℃的冶炼环境下,锌浸出渣中极易产生锌和铅的金属蒸气。通过分析13种冶金渣成分的黏度及熔点,发现3种渣成分(47%SiO₂-23%CaO-30%FeO、40%SiO₂-28%CaO-32%FeO、40%SiO₂-30%CaO-30%FeO,质量分数)具有合适的物理特性,即熔点和黏度分别为1150～1280℃和0.2～0.5 Pa·s。工业实验表明,采用优化的渣成分,锌和铅的回收率分别高达97.3%和94.5%,冶炼后渣内锌和铅的含量分别低至0.51%和0.45%(质量分数)。水淬渣的国标浸出实验表明,浸出液中含1.82 mg/L Zn、～0.01 mg/L Cu、0.0004 mg/L As、～0.01 mg/L Cd、0.08 mg/L Pb和～0.02 mg/L Hg,证实锌浸出渣同步实现无害化...     

基于地球化学的水热还原矿化稳定砷的技术思路

砷作为有色金属矿物的共伴生元素,在有色金属冶炼过程中以含砷“三废”形式大量产出。由于砷具有强致癌性及毒性,导致砷的安全处置问题严重困扰着有色金属冶炼企业。本文通过阐述含砷废水中砷的两种稳定化工艺的研究进展,对比了现有稳定化工艺的优缺点,结合药剂稳定化和矿物稳定化的优点,借鉴砷元素在地球化学中的成矿规律,提出了硫化沉砷?水热还原矿化稳定砷的技术思路。首先采用硫化法脱除含砷废水中的砷,砷的沉淀率高达99.65%,硫化沉淀物在TCLP毒性检测中砷的浓度达到212.9 mg/L。然后采用As-S系一元水热还原矿化法和As-Fe-S系二元水热还原矿化方法稳定砷,稳定化产物分别为雌黄和雌黄?铁硫系(黄铁矿、硫化亚铁)混合物,在TCLP毒性检测中砷的浸出浓度分别为3.86 mg/L和2.65 mg/L。水热还原矿化工艺实现了含砷废水中砷的脱除及稳定化的目的,为水溶液中砷的脱除和稳定化提供了新的思路。     

“双湿法”从汽车失效催化剂中回收铂族金属及有价金属

通过常规湿法浸出-预处理-再次湿法浸出的"双湿法"工艺,综合回收多种汽车失效催化剂(SAC)中的铂族金属(PGMs)及有价金属镧、铈和锆。采用X射线荧光法、分光光度法、ICP-AES法、扫描电镜及X射线衍射进行分析表征。结果表明,"双湿法"工艺可使铂、钯、铑的浸出率比常规湿法浸出分别提高了7%~30%、2%、18%~21%,PGMs的回收率大于95%,浸出渣率为30%~35%;镧、铈和锆同时得到有效回收,其中铈、锆的综合回收率大于92%。     

Activities of liquid Fe-As and Fe-Sb alloys saturated with carbon

A solid iron base alloy of the so-called furnace residue is often formed as a by-product in reduction smelting of lead sinter and scraps with high contents of arsenic and antimony. The use of phase separation into a liquid iron-rich alloy and a liquid lead-rich alloy in lead-iron-arsenic and lead-iron-antimony systems saturated with carbon at relatively low temperatures of about 1200~C was proposed in a new process for treating the fumace residue to recover valuable elements into the lead-rich alloy and fLx toxic arsenic into the iron-rich alloy. As a fundamental study for the proposed process, the activity coefficients and interaction parameters of the Fe-As and Fe-Sb systems saturated with carbon at 1200℃ were derived in this study, based on the determined phase relations in the Fe-Pb-As and Fe-Pb-Sb systems saturated with carbon.