摘要
铅矿通常伴生有铜,在铅火法冶炼过程中,铜进入粗铅。粗铅火法精炼一般采用加硫除铜的方法脱铜,所产浮渣经反射炉溶析后产出三个产品:粗铅、铅冰铜和渣。铅冰铜除含铜外,还含铅、银等元素。迄今,通常采用火法冶金处理这类物料,然而,这种方法存在金属回收率低、环境污染严重、工艺流程长、投资大、成本高等缺点。所以,开发适合于处理该类物料的高效清洁冶金技术具有重要的现实意义。
本论文以铅冰铜及铅冰铜与熔析渣混合料(简称混合料)为物料,在查阅大量资料、对比多种处理方法的基础上首次提出了氧压酸浸——直接电积提铜的全湿法清洁冶金新工艺,并对其中的关键技术进行了理论和试验研究。主要包括以下内容:
1、绘制了423K下的Cu2S-H20系E-PH图和298K下的MeS-H2O系E-pH图,并对铅冰铜和混合料的氧压酸浸过程热力学进行了分析
2、研究了铅冰铜浸出过程工艺条件。系统研究了铅冰铜用新液或电积废液返回氧压酸浸试验工艺条件:浸出时间、氧分压、液固比、矿样粒度、酸量、浸出温度、搅拌速度和浸出溶液中初始Cu2+浓度对铜浸出率和浸出液中铁含量的影响。结果表明:浸出时间、氧分压、酸量、浸出温度和搅拌速度对铜浸出率和浸出液中铁含量有很大影响,液固比、矿样粒度和用于浸出料样的浸出溶液初始Cu2+浓度对铜浸出率和浸出液中铁含量影响不明显。最佳浸出条件为:浸出时间2-3h,氧分压0.8MPa,总压1.2~1.3MPa,酸量理论量(T),浸出温度140~150℃,搅拌速度600rpm,液固比10:1,料样粒度-100目占55%(粗磨料)。在最佳浸出条件下:铜浸出率≥97%,浸出液铁含量<5g/L。渣率~30%,铅入渣率100%,银入渣率>98%,铁入渣率>60%,单质硫产出率~25%。
3、熔析渣中也含有铜,在生产中较难将铅冰铜与熔析渣彻底分开,故最好将铅冰铜与熔析渣合起来考虑(混合料),系统研究了混合料浸出过程工艺条件。混合料含硅高,浸出后料浆过滤很困难。通过试验研究找到了提高过滤性能的方法。用新液浸出时,加复合絮凝剂A。废电积液返回浸出时需要在浸出后向料浆中加入CaC03,调pH至1.5左右,然后加复合絮凝剂A,能很好地解决料浆过滤难的问题。在最佳浸出条件下:矿浆过滤速度220~550 L/m2·h,Cu浸出率>90%,浸出液铁含量<2g/L,渣率55-75%,铅入渣率100%,银入渣率>95%,铁入渣率>80%,单质硫产出率~25%。
4、研究了浸出液直接电积提铜试验。电积最佳工艺技术条件为:极间距4cm,温度25~40℃,电流密度220A/m2,电积液循环速度250L/m3·h,电积终点电积液铜浓度~25g/L,电积液铁含量<10g/L,添加剂20~70g/t·Cu。在此工艺技术条件下,电流效率>90%,槽电压2.0~2.1 V,并得到了符合国标CATH-2要求质量的阴极铜。
5、为验证工艺的稳定性,进行了浸出——电积,电积废液返回浸出的循环试验,共进行了五个循环,取得的技术指标如下:
(1)、铜回收率>97.48%
(2)、渣率~30%
(3)、铅入渣率100%
(4)、银入渣率>97.55%
(5)、铁入渣率>59.68%
(6)、单质硫产出率~23%
6、研究了铅冰铜氧压浸出动力学,建立了料样粒度、总压、浸出温度和酸度对其影响的动力学方程。计算了表观反应活化能:21.03KJ/mol,表明铅冰铜氧压酸浸过程受混合控制。最后建立了铅冰铜氧压浸出铜的数学模型:
α(%)=100×{1-[1-r0/1exp(-1.5856-2608.46T/1+0.646lnP+0.228ln C)t]3}
以65个试验结果检验此模型,吻合甚好。
,论文的创新点为:
(1)、提出了一条处理铅冰铜和混合料的技术路线,研发了从铅冰铜和混合料中回收铜的全湿法冶金新工艺,并申请了发明专利。
(2)、系统研究了反射炉处理粗铅加硫除铜所产生的铅浮渣所产铅冰铜和混合料的氧压酸浸的工艺条件,并得到了高的铜浸出率。
(3)、通过试验找到了解决高硅高铁混合料氧压酸浸料浆过滤难的方法。
(4)、试验研究了低酸溶液体系的直接电积提铜,并获得了符合国标CATH-2要求的阴极铜。
(5)、绘制了423K下的Cu2S-H2O系E-pH图;研究了铅冰铜氧压酸浸的动力学,并建立了料样粒度、总压、浸出温度和酸度对其影响的动力学方程,在此基础上建立了铅冰铜氧压浸出铜的数学模型。
Copper is usually associated with lead minerals, of which enters the lead bullion in the pyrometallurgical process of lead. It's usually separated from the lead bullion in the form of copper sulfide (called Pb-Cu matte) by adding sulfur in the pyro-refining of lead bullion. Pb-Cu matte copper usually contains lead, silver and other valuable metals besides copper. So far, it always treated by pyrometallurgy which has a lot of disadvantages such as low recovery of metals, high environmental pollution, long flow, high investment and cost etc. Therefore, the development of a high efficiency and cleaning metallurgical technology to treat such materials has important practical significance.
It takes Pb-Cu matte and mixed materials as materials in experiments. A new technology of hydrometallurgy for treating such materials by pressure oxidative leaching and electrowinning directly is proposed, and the theory and experiment of the key process were investigated. The main contents of the paper contain as follows:
1. The thermodynamics of pressure oxidative leaching of Pb-Cu matte and mixed materials was analyzed by the E-pH diagrams of Cu2S-H2O system at 423K and MeS-H2O system at 298K.
2. The leaching conditions of Pb-Cu matte were studied. The effects of leaching time, oxygen partial pressure, L/S ratio, materials granularity, acid addition, leaching temperature, agitation speed and initial Cu2+ concentration on the extraction of copper and iron at pressure oxidative leaching of Pb-Cu matte by new solution which no Cu2+ and waste electrolyte were investigated systematically. The effect of initial Cu2+ concentration, L/S ratio and materials granularity are insignificant compared to the other reaction parameters. The best found conditions are: leaching time 2~3 h, oxygen partial pressure 0.8 MPa, total pressure 1.2~1.3 MPa, acid addition theoretical mass, leaching temperature 140~150℃, agitation speed 600 rpm, L/S ratio 10:1 and materials granularity 55% smaller than -100 mesh. Under these conditions,>97% Cu is extracted with the concentration of iron in solution<5g/L. The leaching residue is about 30% of the initial mass, the recovery of lead and silver is close to 100% and 98% respectively, the iron is more than 60% as deposition in residue and the yield of sulfur is about 25% of total sulfur mass.
3. It is very difficult to separate Pb-Cu matte from slag which contains copper in the pyrometallurgical process of lead. So, it has to put the Pb-Cu matte and slag (called mixed materials) together into considered. The pressure oxidative leaching of mixed materials with high silicon was studied systematically. The filtration of magma is very difficulty after Pox leaching. The technique for improving the filtration performance is achieved by experiments. It can resolve the difficulty of the filtration by adding composition flocculation reagent A, CaCO3 and composition flocculation reagent A after the leaching by new solution and waste electrolyte respectively. Under the best conditions, the filtration rate is 220~550 L/m2·h, the Cu extraction is more than 90% with the concentration of iron in solution <2g/L, the leaching residue is about 55~75% of the initial mass, the recovery of lead and silver is close to 100% and 95% respectively, the iron is more than 80% as deposition in residue and the yield of sulfur is about 25% of total sulfur mass.
4. The experiment of copper electrowinning was studied. The best found conditions are:the pole pitch 4cm, the temperature 25~40℃, the current density 220A/m2, the circuit speed of the electrolyte 250L/m3·h, the terminal copper content of the waste electrolyte 25g/L, the concentration of iron <10g/L and the amount of additive is 20-70g/t·Cu. Under these conditions, the current efficiency is greater than 90%, the tank voltage is 2.0-2.1V and the cathode copper are up to CATH-2.
5. In order to prove the stability of the process, the circulation experiments of leaching, electrowinning and leaching by waste electrolyte were carried out. It achieves some parameters through 5 circulation experiments.
(1). Cu extraction rate >97.48%
(2). Yield of residues~30%
(3). Lead recovery rate 100%
(4). Silver recovery rate >97.55%
(5). Iron as deposition >59.68%
(6). Yield of sulfur~23%
6. The kinetics of pressure oxidative leaching of Pb-Cu matte was studied. The kinetics equations of materials granularity, total pressure, leaching temperature and acidity are found respectively. The apparent reaction activation energy is 21.03KJ/mol which indicates that the pressure oxidative leaching of Pb-Cu matte is driven by mix-controlled. The mathematics model of Cu extraction from Pb-Cu matte by pressure oxidative leaching is found.
a(%)=100×{1-[1-1/r0exp(-1.5856-2608.461/T+0.6461n P+0.2281nC)t]3}
The model was proved by 65 experiments. It indicates that the calculated consequences and experimental consequences are inosculation very well.
The innovations of the paper are as follows:
(1). A new technology route for Pb-Cu matte and mixed materials is proposed. A new process of hydrometallurgy for Cu extraction from Pb-Cu matte and mixed materials is researched and developed, and the patent is applied also.
(2). The technology conditions of pressure oxidative leaching of Pb-Cu matte and mixed materials were investigated systematically. It achieves high copper extraction rate.
(3). The technique for improving the filtration performance of magma which is very difficult filtration after Pox leaching of mixed materials with high silicon and iron is achieved by experiments.
(4). The copper electrowinning of low acidity solution was studied and the cathode copper which is up to CATH-2 is achieved.
(5). The E-pH diagrams of Cu2S-H2O system at 423K is constructed firstly. The kinetics of pressure oxidative leaching of Pb-Cu matte was studied. The kinetics equations of ore granularity, total pressure, leaching temperature and acidity are found respectively. The mathematics model of Cu extraction from Pb-Cu matte by pressure oxidative leaching is found.
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