Electrowinning anodes

Because of the unique properties of lead to exist in three valence states (metal, ion with +2 charge, and ion with a +4 charge), lead is used not only for electrochemical anodes to electroplate other metals from sulfuric acid solution but also to serve as anode, cathode, and active material in lead acid storage batteries. Storage batteries represent over 60% of lead usage worldwide and over 80% of lead usage in the United States. Electrowinning anodes and batteries are two of the unique successes of lead product development efforts. 

Anodes. Lead—antimony (6—10 wt %) alloys containing 0.5—1.0 wt % arsenic have been used widely as anodes in copper, nickel, and chromium electrowinning and metal plating processes. Lead—antimony anodes have high strength and develop a corrosion-resistant protective layer of lead dioxide during use. Lead—antimony anodes are resistant to passivation when the current is frequendy intermpted. 

Lea.dAnodes. A principal use for lead—calcium—tin alloys is lead anodes for electrowinning. The lead—calcium anodes form a hard, adherent lead dioxide layer during use, resist corrosion, and gready reduce lead contamination of the cathode. Anodes produced from cast lead—calcium (0.03—0.09 wt %) alloys have a tendency to warp owing to low mechanical strength and casting defects. 

Other Metals. AH the sodium metal produced comes from electrolysis of sodium chloride melts in Downs ceUs. The ceU consists of a cylindrical steel cathode separated from the graphite anode by a perforated steel diaphragm. Lithium is also produced by electrolysis of the chloride in a process similar to that used for sodium. The other alkaH and alkaHne-earth metals can be electrowon from molten chlorides, but thermochemical reduction is preferred commercially. The rare earths can also be electrowon but only the mixture known as mischmetal is prepared in tonnage quantity by electrochemical means. In addition, beryIHum and boron are produced by electrolysis on a commercial scale in the order of a few hundred t/yr. Processes have been developed for electrowinning titanium, tantalum, and niobium from molten salts. These metals, however, are obtained as a powdery deposit which is not easily separated from the electrolyte so that further purification is required. 

Fused-salt electrolysis of K2NbFy is not an economically feasible process because of the low current efficiency (31). However, electrowinning has been used to obtain niobium from molten alkaU haUde electrolytes (32). The oxide is dissolved in molten alkaU haUde and is deposited in a molten metal cathode, either cadmium or zinc. The reaction is carried out in a ceramic or glass container using a carbon anode the niobium alloys with the cathode metal, from which it is freed by vacuum distillation, and the niobium powder is left behind. 

Adding teUurium to lead and to lead aUoyed with sUver and arsenic improves the creep strength and the charging capacity of storage battery electrodes (see Batteries). These aUoys have also been suggested for use as insoluble anodes in electrowinning. 

Fig. 7. Sections of metal electrowinning ceU without diaphragm (a), end view (b), side view where A is anode and C is cathode.

In the field of electrowinning and electrorefining of metals, titanium has an advantage as a cathode, upon which copper particularly can be deposited with finely balanced adhesion that allows the electrodeposited metal to strip easily when required. Titanium anodes are also being employed as a replacement for lead or graphite in the production of electrolytic manganese dioxide. 

Besides copper passing into the solution as ions, the total concentration of the solution in respect of S04 ions (not discharged) and Cu2+ ions (copper is depositing on the cathode) remains constant. The electrolysis merely transfers copper from the anode to the cathode. With a platinum or a carbon anode, it is found that the color of the solution fades as copper is deposited, whereas with copper electrodes, the color does not change. The two situations, in fact, represent respectively the electrowinning and the electrorefining processes introduced later in the section on process classification. 

In the aluminum electrowinning process a phenomenon called the anode effect is normally encountered when the alumina content in the electrolyte falls below 2%. The anode gets partially covered with a gas blanket and as a consequence, sparking occurs and the cell voltage fluctuates considerably due to frequent breaking and reestablishment of local contact between the anode and the electrolyte. A heavy current passes through the anode area... 

The electrowinning processes essentially use anodes that do not dissolve anodically. In electrorefining, however, an impure metal is anodically dissolved as metal ions and subsequently these ions are reduced at the cathode to yield the pure metal the cell reactions are ... 

The anode potential is so positive, due principally to the activation overpotential, that the majority of the impurity metals (Fe, Cu, Co, etc.) in the anode dissolve with the nickel sulfide. In addition, some oxygen is evolved (2 H20 = 02 + 4 H+ + 4 e ). The anodic current efficiency reduced to about 95% on account of this reaction. Small amounts of selenium and the precious metals remain undissolved in the anode slime along with sulfur. The anolyte contains impurities (Cu, Fe, Co) and, due to hydrogen ion (H+) liberation, it has a low pH of 1.9. The electrolyte of this type is highly unfit for nickel electrowinning. It is... 

Zinc electrowinning takes place in an electrolytic cell and involves running an electric current from a lead-silver alloy anode through the aqueous zinc solution. This process charges the suspended zinc and forces it to deposit onto an aluminum cathode (a plate with an opposite charge) that is immersed in the solution. Every 24 to 48 h, each cell is shut down, the zinc-coated cathodes removed and rinsed, and the zinc mechanically stripped from the aluminum plates. The zinc concentrate is then melted and cast into ingots, and is often as high as 99.995% pure. 

Zinc electrowinning Zinc in a sulfuric acid/ aqueous solution, lead-silver alloy anodes, aluminum cathodes, barium carbonate, or strontium, colloidal additives... 

In copper electrolysis, there are only a very limited number of impurities that will cause a current efficiency decrease, and these occur particularly in electrowinning. One troublesome impurity is iron, as the ferric ion is preferentially reduced at the cathode to ferrous ion. The ferrous ion is subsequently reoxidized at the anode. The actual current efficiency obtained is dependent on the iron concentration. (8 ) For example, an electrolyte containing 10 gpl iron gives a 77% current efficiency, but with 1 gpl, a 90% value can be obtained. 

It consists in a deposition of ions from an electrolyte onto the cathode in an electrolytic cell, under the influence of an applied potential. Usually the process is accompanied by material dissolution from the anode. The electrowinning from aqueous solutions is an important commercial method for the production (and/or refinement) of many metals, including, for instance, chromium, nickel, copper, zinc. As for the electrodeposition from non-aqueous solutions, the primary production of aluminium, electrodeposited from a solution of A1203 in molten cryolite, is a typical example. Other metals which may be regularly reduced in a similar way are Li, Na, K, Mg, Ca, Nb, Ta, etc. 

Electrowinning is an electrolytic process where cathodic reduction is used to recover metal from an electrolyte using an inert anode. The process differs from electro-refining where the anodic reaction is dissolution of the metal, that is then reversed at the cathode. 

Lead-cobalt anodes used for electrowinning of zinc from sulfate solutions were investigated by Rashkov et al. [404]. 

---