摘要
Zn、Cu、Ni、Co、Mn等金属的湿法冶金工业中,电积工序一般采用含高浓度H2S04的电解液,因而只能采用Pb合金阳极。但Pb合金阳极存在析氧过电位高、表面氧化膜疏松易脱落、密度大、易蠕变等问题,造成电积过程的能耗高、阴极产品易受Pb污染。针对上述问题开发的电催化涂层阳极(DSA)、多元Pb合金阳极及多孔阳极,虽然分别在某些方面取得了较好效果,但仍不能满足工业应用要求。
论文借鉴相关领域的最新研究成果,以开发低成本、高性能新型复合多孔Pb合金阳极为目标,深入研究了多孔Pb合金阳极在H2S04电解液中的电化学行为,研究了“反三明治”结构对多孔Pb合金阳极的阳极电位、腐蚀率、导电性及力学性能的影响,研究了RE添加对Pb合金阳极结构与性能的影响,研究了复合多孔Pb合金阳极在锌电积和铜粉电积中的应用关键技术,开发了工业尺寸复合多孔Pb合金阳极的反重力渗流铸造设备与工艺,采用复合多孔Pb合金阳极在锌电积工业现场开展了工业电解试验。主要创新性成果如下：
(1)研究了多孔Pb合金阳极在H2S04溶液中的电化学行为,明确了多孔结构对阳极表面氧化膜的形成过程、膜层组分与结构、电极内部传质传荷特点及阳极析氧机制的影响,多孔阳极内部的传质与传荷平行进行,电化学反应强度从外到内依次减弱,电化学“特征深度”约为3mm。计算了多孔阳极电化学反应有效面积和表观活化能,揭示了多孔阳极节能降耗的电化学本质,其表观活化能较传统阳极增加约5kJ/mol,但电化学反应有效面积为传统阳极的10倍左右,使得析氧过程的表观交换电流密度大,析氧能力增强。
(2)提出并制备了“反三明治”结构复合多孔Pb合金阳极,实现了金属芯板与多孔层的冶金结合。复合多孔阳极的芯板主要起传导电流和承担载荷的作用,而电化学性能靠外侧多孔层发挥。当芯板为2mm厚时,孔径为1.25-1.43mm的Pb-Ag合金复合多孔阳极的极限抗拉强度和导电率分别为同孔径纯多孔阳极的3倍和1.3倍。与传统平板阳极和多孔阳极比较,复合多孔阳极的阳极电位降低114mV和16mV,腐蚀率降低48.7%和6.3%,同时抗拉强度和导电率较多孔阳极提高200%和30%。
(3)揭示了Nd、Pr、Gd和Sm对Pb合金的组织结构、氧化膜结构以及析氧过程的影响规律,获得了适用于湿法冶金电沉积的Pb-Ag(0.6wt.%)-Nd(0.5wt.%)三元合金阳极,其极限抗拉强度、稳定阳极电位和腐蚀率分别为20.985MPa.1.798V和2.347g/(m2h),分别是传统Pb-Ag(0.8%)平板阳极的113.9%、99.7%和59.9%。
(4)研发了复合多孔Pb合金阳极在锌电积和铜粉电积中的工业应用技术,采用975mm×620mm×6mm的复合多孔阳极开展了为期24天的锌电积工业试验。与传统平板阳极比较,阳极电位、槽电压和能耗平均降低91mV、116mV和85kWh/t-Zn,腐蚀率、阳极泥及电锌Pb含量分别降低82.5%、77%和34.4%。
In the hydrometallurgical process of nonferrous metals such as Zn, Cu, Ni, Co, Mn, the high-concentration H2SO4solution is always used and Pb-based alloys are generally used as anodes. It can meet the basic requirements, but still has problems such as high oxygen evolution over-potential, unsatisfactory corrosion resistance, heavy and easy creep, which may result in high energy consumption and lead contamination of the cathode products. In order to save these problems, research has been done, mainly focused on electrocatalytic coated anodes(DSA), Pb-based multi-component alloy anodes and porous anodes. There are certain progress but still cannot meet the industrial requirements,
In order to develop low cost and high performance new composite porous anode(CPA), by adopting the latest research results in related field, the electrochemical behavior of porous anode in H2SO4electrolyte, the influence of "anti-sandwich structure" on anodic potential, anodic corrosion rate, electric conductivity and mechanical properties, and the influence of RE elements on the structure and performance of Pb-based alloys are studied. After that, the counter-gravity infiltration equipment and technologies of industrial-sized composite porous anode are developed, and then the industrial test at zinc electro winning industrial site is carried out. The main research results are as follows:
(1) The electrochemical behavior of CPA in H2SO4electrolyte is studied, and the forming process, structure and component of the oxidation film, the charateristic of mass transfer and charge transfer, and the oxygen evolution mechanism of it are revealed. Inside the porous anode, mass transfer and charge transfer are parallel processes, and the electrochemical reaction strength decreases from outside to inside, the "characteristic depth" is about3mm when the pore diameter is1.43-1.60mm. The electrochemical surface area and apparent activation energy are caculated, and the electrochemical nature of energy-saving performance is indicated. The apparent activation energy of CPA is about5kJ/mol more than traditional flat plate anode, but its electrochemical surface area is about10times of the later, which can enlarge the apparent exchange current, and enhance the oxygen evolution capability.
(2) The "anti-sandwich structure" composite porous anode, with the core of dense metal and two pieces of porous layers metallurgical bonding together, is designed and prepared. The core board of the composite porous anode mainly takes the role of conducting current and taking load, and the electrochemical performance depends on the lateral porous layer. When the core board is2mm thick, the ultimate tensile strength and conductivity of CPA with pore diameter of1.25-1.43mm are3times and1.3times respectively than that of pure porous anode for the same pore diameter. Compared with traditional flat anodes and pure porous anodes, its anodic potential is114mV and16mV lower, and its corrosion rate is48.7%and6.3less, respectively.
(3) The influences of Gd、Pr、Nd、Sm on the metallographic structure, oxidation film and mechanism of the oxygen evolution process are revealed, and a new kind of Pb-Ag (0.6wt.%)-Nd (0.5wt.%) ternary alloy suits for the electro winning process is obtained. The ultimate tensile strength, stable anodic potential and corrosion rate are20.985MPa、1.798V and2.347g/(m2h), which is respectively113.9%,99.7%and59.9%of the traditional Pb-Ag(0.8wt.%) anode.
(4) The industrial application technologies of composite porous anode in zinc electrolytic process and copper powder electrolytic process are studied and developed, and the24-day industrial test using975mm×620mm×6mm CPAs is carried out in the zinc electrolyzing plant. The anodic potential, cell voltage and energy consumption are91mV,116mV and85kWh/t-Zn lower than traditional flat plate anode, and corrosion rate, formation of anode slime and Pb in zinc product are respectively82.5%,77%and34.4%less.
引文
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