铜顶吹熔炼过程中砷元素的走向调控研究

随着铜精矿品位逐渐下降,精矿中的杂质元素越来越多,其中有害元素砷在冶炼过程中很难脱除,且在铜熔炼系统中循环累积,最终影响阴极铜的质量。某冶炼企业铜顶吹熔炼生产实践中,有害砷元素在烟尘中的分配比例为55%～75%,在铜锍相中分配比例为5%～15%,在渣相中分配比例为20%～35%。本文主要对铜顶吹熔炼过程中砷的分布与走向调控手段进行了理论分析,并在实验室条件下探究了熔渣中Fe/SiO₂、富氧浓度、铜锍品位、渣中CaO含量等工艺参数对不同产出物中砷分配率的影响规律,获得了砷进入渣相的有效调控措施。优化工艺参数后,As在渣中占比为30%～40%,烟尘中占比为50%～60%,铜锍中占比为10%～20%,解决了铜冶炼过程砷进入硫酸系统形成大量污酸的问题,从而控制各个产品中砷的含量。     

白烟尘两段逆流浸出工艺研究

针对白烟尘既富含铜、铅、锌、铋等多种有价金属，又含有砷、镉等有害元素的特点，提出一种两段逆流浸出工艺。采用该工艺进行实验处理某铜冶炼厂生产的白烟尘，分别考察了酸浸方式、初始硫酸质量浓度、酸浸液固比、酸浸温度、酸浸时间对铜砷浸出的影响。探索出最佳工艺条件液固比为4∶1，初始硫酸质量浓度80g/L，反应温度为80℃，反应时间为2 h。二次浸出液返回继续浸出白烟尘，此时白烟尘铜、锌、砷浸出率分别为95.7%、98.5%、92.2%，而浸出渣中铜、锌、砷品位降至0.42%、0.50%、1.28%。铅、铋的品位实现有效富集，二次酸浸渣中品位分别为47.73%和9.72%，相比原料分别富集约2.6倍和4.5倍。     

浅析砷锑在铜电解过程中的行为

通过对铜电解过程中阳极铜、阳极泥、砷锑渣、电解液悬浮物、电铜中杂质元素存在形态的分析 ,探讨砷锑在铜电解过程中的行为 ,以寻求稳定铜电解生产过程和提高电铜质量的方法     

底吹连续炼铜过程中砷的走向及控制

火法炼铜原料——铜精矿品位逐渐下降,杂质含量逐渐增多,其中有害元素砷不易去除,在系统中不断积累,严重影响最终阴极铜质量。据某公司生产统计分析,砷元素在气相中的分配比例为53%～89%,在铜锍相中分配比例为4%～19%,在渣相中分配比例为7%～28%。据此,该公司从入炉原料成分,熔炼阶段铜锍品位、氧浓及氧矿比,吹炼阶段铜锍品位、含砷量及铁硅比,精炼阶段的操作及脱砷剂的要求方面作了调控,调控后阴极铜产品中的砷含量得到了有效控制。     

浅析砷锑在铜电解过程中的地为

通过对铜电解过程中阳极铜，阳极泥，砷锑渣，电解液悬浮物，电铜中杂质元素存在形态的分析，探讨砷锑在铜电解过程中的行为，以寻求稳定铜电解生产过程和提高电铜质量的方法。     

富氧侧吹熔炼-多枪顶吹吹炼炼铜工艺杂质元素行为

通过对富氧侧吹熔炼-多枪顶吹吹炼炼铜工艺过程的生产数据进行整理,计算得出了铁、锌、铅和砷在整个系统的分布率。通过XRD、SEM/EDS等测试手段,对冰铜、熔炼渣和吹炼渣等部分中间产物的物相组成和微观结构进行了表征。综合分析了主要杂质元素铁、锌、铅和砷在富氧侧吹熔炼-多枪顶吹吹炼炼铜工艺中的分布行为规律。结果表明,铁主要以铁橄榄石、铁酸锌、铁酸铜等形式分布于炉渣中,锌绝大部分也会造渣并以铁酸锌的形式进入炉渣,即大部分铁和锌能在炉渣中直接开路除去;而大部分铅和砷进入炉渣和烟尘中,可通过渣的形式及挥发机理脱除和回收,但还有相当数量的铅和砷会残留于粗铜中,只能在后续电解工序中脱除。总结了这几种杂质元素减量化控制的有效方法和途径,为铜冶炼过程中杂质元素的综合处理和稳定生产提供了参考。     

铜冶炼烟尘选择性湿法脱砷及有价元素的同步回收

针对铜冶炼系统含砷烟尘中砷难以高效富集和脱除的问题,采用水浸-碱浸两步浸出工艺进行脱砷研究。结果表明：含砷烟尘先在液固比1∶1的条件下常温水浸,然后在NaOH浓度2 mol/L、Na₂S浓度0.2 mol/L、温度70℃、液固比4∶1的条件下碱浸,最终砷的平均浸出率为96.27%,浸出渣含砷量小于0.5%,铜、铁、锌、铅的平均浸出率分别为0.01%、0.01%、4.72%和11.17%。     

铜转炉烟尘选冶联合处理新工艺研究

采用选冶联合方法处理铜转炉烟尘 ,烟尘经水浸、固液分离后 ,浸出液用湿法操作脱除杂质铁、砷 ,以海绵铜的形式回收有价金属铜 ,以ZnSO·7H2 O的形式回收有价金属锌 ;浸出渣则通过摇床选出铜精矿、次精矿和中矿直接返回转炉     

重铬酸钾氧化-硫酸亚铁铵返滴定法测定铜闪速冶炼烟尘中砷

准确测定铜闪速冶炼烟尘中的砷对于炉前配料的计算和生产控制具有重要的作用。采用硝酸-氯酸钾饱和溶液、氟化铵溶液、高氯酸溶解样品,再用硫酸(1+1)驱除硝酸后,在盐酸介质中以硫酸铜为催化剂,用次亚磷酸钠把溶液中的砷离子还原为单质砷,过滤分离其他杂质。以过量的重铬酸钾标准滴定溶液溶解单质砷,以N-苯代邻氨基苯甲酸溶液为指示剂,用硫酸亚铁铵标准滴定溶液滴定过量的重铬酸钾标准滴定溶液,建立了硫酸亚铁铵返滴定法测定铜闪速冶炼烟尘中砷的方法。采用次亚磷酸钠将溶液中的砷还原为单质砷沉淀时,可能会有部分砷因未被还原而被过滤到溶液中,试验考察了滤液中残存的砷量对砷测定结果的影响。研究表明,滤液中砷的质量分数小于0.01%,相对于样品中的砷可以忽略不计。共存元素的干扰试验表明,样品中共存的铜、铅、铁、锌等元素对砷测定的影响可忽略不计。将实验方法应用于测定3个铜闪速冶炼烟尘样品中的砷,并进行加标回收试验,测定结果的相对标准偏差(RSD,n=11)在0.35%～2.6%之间,加标回收率在99%～101%之间。采用实验方法测定2个铜闪速冶炼烟尘样品中的砷,测定结果与微波消解-电感耦合等离子体原子发射光谱法(ICP-AES)相符。     

重铬酸钾氧化-硫酸亚铁铵返滴定法测定铜闪速冶炼烟尘中砷

准确测定铜闪速冶炼烟尘中的砷对于炉前配料的计算和生产控制具有重要的作用。采用硝酸-氯酸钾饱和溶液、氟化铵溶液、高氯酸溶解样品,再用硫酸(1+1)驱除硝酸后,在盐酸介质中以硫酸铜为催化剂,用次亚磷酸钠把溶液中的砷离子还原为单质砷,过滤分离其他杂质。以过量的重铬酸钾标准滴定溶液溶解单质砷,以N-苯代邻氨基苯甲酸溶液为指示剂,用硫酸亚铁铵标准滴定溶液滴定过量的重铬酸钾标准滴定溶液,建立了硫酸亚铁铵返滴定法测定铜闪速冶炼烟尘中砷的方法。采用次亚磷酸钠将溶液中的砷还原为单质砷沉淀时,可能会有部分砷因未被还原而被过滤到溶液中,试验考察了滤液中残存的砷量对砷测定结果的影响。研究表明,滤液中砷的质量分数小于0.01%,相对于样品中的砷可以忽略不计。共存元素的干扰试验表明,样品中共存的铜、铅、铁、锌等元素对砷测定的影响可忽略不计。将实验方法应用于测定3个铜闪速冶炼烟尘样品中的砷,并进行加标回收试验,测定结果的相对标准偏差(RSD,n=11)在0.35%～2.6%之间,加标回收率在99%～101%之间。采用实验方法测定2个铜闪速冶炼烟尘样品中的砷,测定结果与微波消解-电感耦合等离子体原子发射光谱法(ICP-AES)相符。     

Activities of As,Sb, Bi,and Pb in copper mattes—impurity elimination

The theoretical possibilities for the elimination of As, Sb, Bi, and Pb from copper matte were evaluated on the basis of the activity behavior of these impurity elements in the matte, considering removal by purge gas blowing, chlorination, vacuum evaporation, and slagging. The calculations were made assuming equilibrium conditions between the prevailing phases and using different combinations of sulfur, oxygen, and chlorine potentials. Present evaluations show that (1) As can be evaporated from the matte, using moderate amounts of purge gas at a high sulfur pressure of about 10⁻² atm (1013.3 Pa) and a temperature of 1200°C (1473. 15 K); (2) Sb, Bi, and Pb can also be eliminated under similar conditions using a chloridizing purge gas; (3) the purge gas, consumption can be decreased by lowering the total pressure of the system; (4) on a thermodynamic basis, the vacuum evaporation rates of these impurity elements should be much higher from the matte than from copper, the actual differences not, however, having been so apparent in previously published experimental studies, due possibly to kinetic reasons; and (5) the distribution coefficients of As and Sb between slag and matte increase along with the sulfur pressure, although not sufficiently to utilize this phenomenon on an industrial scale. A. ROINE, formerly with Institution of Process Metallurgy, Helsinki University of Technology, SF-02150, ESPOO, Finland     

渣中铁硅比对铜熔炼中伴生元素行为的影响

利用已开发的铜冶炼过程的计算机模型，模拟研究了渣中铁硅比对伴生元素Ni、Co、Sn、Ph、Zn、As、Sb和Bi在铜冶炼体系中分配行为的影响。研究表明：提高中铁硅比，不利于伴生元素在渣中的脱除。     

铜电解阳极钝化及漂浮阳极泥控制技术研究进展

阳极钝化和漂浮阳极泥是影响铜电解精炼稳定生产的主要因素,会造成生产能力的损失、电耗增加、阴极铜质量下降等问题,其形成的主要原因是阳极铜和电解液中含有杂质.目前文献表述中关于阳极钝化的形成机理包括:砷含量对阳极钝化有促进或抑制作用;阳极铜表面生成CuSO4盐膜引起钝化;氧化亚铜与锌粉共同作用引起钝化;氧化亚铜和硫酸铜晶体...     

电感耦合等离子体原子发射光谱法测定纯铜中微量元素

以硝酸溶解样品,采用电感耦合等离子体原子发射光谱(ICP-AES)法测定纯铜中As、Bi、Zn、Sb、Pb、Fe、Sn、Ni等八种微量杂质元素的含量。通过试验选择各元素最佳分析谱线,并对基体干扰及共存元素之间的干扰进行探讨。在选定的实验条件下,方法的检出限为2.0~14.4ng/L,样品加标试验回收率在96%~102%之间。结果表明,用本法测定标准样品中8种元素的含量,测定值与认定值相符,相对标准偏差(RSD)均小于6%。     

Mineralogical characterization of a copper anode and the anode slimes from the la caridad copper refinery of mexicana de cobre

A detailed mineralogical study was carried out to characterize a copper anode, the anode-face slimes, the slimes on the bottom of the refining cell, and the autoclave-leached slimes from the La Caridad refinery of Mexicana de Cobre. The objective was to identify possible Pb-Sb-Bi and As-Sb-Bi interactions that could control the Sb and Bi concentrations of the electrolyte. Although some Pb, As, Sb, and Bi can be found in solid solution in the copper crystals of the anode, these elements are mostly present as Cu-Pb-As oxide and Cu-Pb-As-Sb-Bi oxide inclusions at the grain boundaries. During electrorefining, the Pb, As, Sb, and Bi in solid solution dissolve. Part of the Pb, As, Sb, and Bi in the oxide inclusions also dissolves, but part reacts in situ to form PbSO₄ and Pb₅(AsO₄)₃(OH,Cl). Some of the dissolved elements reprecipitate as PbSO₄, SbAsO₄, Sb-As oxide, Sb-As-Bi oxide, Pb₅(AsO₄)₃(OH,Cl), and an oxidate phase of mainly Cu-Ag-AsO₄-SO₄ composition. Thus, high As contents facilitate the precipitation of Sb and Bi from the electrolyte. Although Pb-Sb oxide and Pb-Bi oxide species were only rarely detected, a high Pb content in the anode may retard the dissolution of the Cu-Pb-As-Sb-Bi oxide inclusions, thereby retaining some Sb and Bi in the raw anode slimes. Autoclave leaching dissolves part of As, Sb, and Bi, but the SbAsO₄ and Sb-As-Bi oxide species remain in the leach residue. The Pb is converted almost entirely to PbSO₄, which is present as subhedral crystals in the autoclave leach residue.     

Thermodynamics of Copper Matte Converting: Part II. Distribution of Au,Ag, Pb,Zn, Ni,Se, Te,Bi, Sb and As Between Copper,Matte and Slag in the Noranda Process

The solubility of minor elements in fayalitic slags was assessed thermodynamically assuming exclusively oxidic dissolution for Pb, Zn and Ni, metallic dissolution for Au and Ag, molecular and monatomic dissolution for Se and Te, and monatomic dissolution for Bi, Sb and As. Based on these assumptions as well as the thermochemical data in the literature, an analytical method was developed to calculate the distribution equilibria of minor elements between copper, matte and slag phases. As an example of the application, the method was demonstrated for the analysis of behavior of minor elements in the Noranda Process producing metallic copper or high grade matte. The distribution of minor elements was expressed in terms of concentration ratios of an element for copper/matte, copper/slag and matte/slag phases. Using the concentration ratios and also formulae compensating for mechanical suspension, apparent distribution coefficients of the minor elements in the actual process were calculated as a function of the process parameters: temperature, partial pressure of SO₂, magnetite activity and matte grade. An excellent agreement was observed between the calculated and observed data, thus providing logical basis for interpreting operating data of the Noranda Process. The behavior of minor elements under various operating conditions can also be predicted by the present model.     

真空法从粗铟中脱除镉锌铋铊铅的研究

介绍了采用真空法从粗铟中直接脱除镉、锌、铊、铅、铋取代传统试剂法脱除杂质的方法。从理论上分析了铟与上述杂质分离的可能性，并进行了温度、蒸馏时间、真空度、投料量等的条件实验和综合条件实验。结果表明，粗铟中镉、锌、铋、铊可除至高纯铟要求，铅可大部分除去。该方法是粗铟精炼中流程短、无污染、无中间渣、低能耗的新工艺、新技术。     

富氧底吹炼铅氧化熔炼元素分配热力学模拟

基于最小吉布斯自由能原理,模拟计算了铅精矿富氧底吹炼铅工艺氧化熔炼段的元素分配行为,并与半工业试验数据进行对比。在典型工业富氧底吹炼铅工艺参数条件下,重点考察了氧料比对Pb、Cu、As、Sb、Bi等元素分配行为的影响。计算结果表明,Pb、Cu、As、Sb和Bi在渣相中的分配率随氧料比的提高而增加。当氧料比为175kg/t时,Pb、Cu、Sb和Bi在金属相、渣相和气相中的分配比例基本符合半工业试验统计数据,但As计算结果与半工业数据存在一定偏差,原因可能是由于缺乏精确的活度系数。     

Effects of CaO, Al2O3, and MgO additions on the copper solubility, ferric/ferrous ratio, and minor-element behavior of iron-silicate slags

The effects of CaO, Al₂O₃, and MgO additions, singly or in combination, on the copper solubility, the Fe³⁺/Fe²⁺ ratio in slag, and on the minor-element behavior of silica-saturated iron silicate slags were examined at 1250 °C and a p _O2 of 10⁻¹² to 10⁻⁶ atm. The results indicated that copper solubility in slag was lowered with the addition of CaO, MgO, and Al₂O₃, in decreasing order. The Fe³⁺/Fe²⁺ ratio in the slag decreased with the additions, but this effect was smaller at lower oxygen potentials. The presence of small amounts (about 4 pct) of CaO, Al₂O₃, and MgO in the slag resulted in increased absorption of Bi and Sb into molten copper, but had a smaller effect at large additions (about 8 to 11 pct). The distribution behavior of Pb was a function of oxygen partial pressure, which indicates the oxidic dissolution of Pb in the slag as PbO, while the behavior of Bi, Sb, and As was found to be independent of oxygen potential, supporting the atomic (neutral) dissolution hypothesis of these elements in the slag. The distribution behavior of Pb and As was not significantly affected by the additions. The activity coefficients of Bi and Sb in the slags were determined to be as follows: (1) for no addition, γ _Bi=40 and γ _Sb=0.4; (2) for small additions (about 4.4 pct), γ _Bi=70 to 85 and γ _Sb=0.8; and (3) for large additions (about 8 to 11 pct), γ _Bi=60 to 75 and γ _Sb=0.5 to 0.7.     

Kinetics of As,Sb, Bi and Pb volatilization from industrial copper matte during Ar+O<Subscript>2</Subscript> bubbling

A kinetic study on minor elements removal during copper matte oxidation was designed under the presumptions of low FeO activity and of no fayalite slag formation. Copper matte with a mass fraction of Cu of 59 pct was mixed by Ar gas blowing during preheating. The matte was oxidized at 1523 and 1673 K by bubbling Ar+O₂ gas through a submerged nozzle. The effects of melt temperature and input oxygen content on the oxidation rate of matte and the volatilization rate of minor elements in copper matte are discussed. The competition reaction composed of the oxygen dissolution into matte and SO₂ gas evolution rate results in the preferential oxidation of FeS in copper matte. The desulfurization rate of matte and the volatilization of minor elements in copper matte were primarily controlled by the mass-transfer rate through the gas film boundary layer around rising gas bubbles. The As, Pb, and Bi were significantly removed during Ar gas blowing with the volatilization rates of Bi and Pb markedly increasing with the melt temperature. However, the dependences of the volatilization rates on the input oxygen partial pressure were affected in a complicated way by the effects of the melt temperature and the reduced amount of exhaust gas.