NEW TECHNOLOGY FOR LEAD

The Hydrometallurgy of Lead

Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering Laval University, Quebec City, Canada G1V 0A6 e-mail: Fathi.Habashi@arul.ulaval.ca

ABSTRACT Lead is an ancient metal, has been produced to-date from its ores exclusively by pyrometallurgical route. The process suffers from high operating cost and excessive pollution problems. Extensive research has been going on since the beginning of the twentieth century to find a non-polluting process for its production and a solution for its complex refining scheme. It has been assumed correctly that the hydrometallurgical route should be the most promising. Pilot plants have been constructed and operated for a reasonable periods, but no process has proved to be fully satisfactory. As a result, a number of smelters and refineries have been shut down. The present review analyzes the situation and suggests that the best route to treat lead sulfide concentrates is by leaching with fluoroboric acid, HBF4, containing ferric fluoroborate, Fe(BF4)3, and electrolyzing the solution in a diaphragm cell - - a process recently invented by Italian metallurgists. In this process, any silver present in the concentrate remains in the residue together with elemental sulfur and can be recovered by known methods.

INTRODUCTION Lead has been produced for thousands of years exclusively by thermal methods. The complex refining steps and the pollution in the neighborhood of smelters are causing much trouble to the nearby population. For example, the high content of lead in crab collected from the ocean in the vicinity of a lead smelter worries consumers. The appreciable amounts of lead in wine produced from a vineyard near a lead smelter causes concern to the industry. The maximum permissible limit for lead in the vicinity of a smelter is 0.05 mg Pb/m3 of air or 6 ppb, a limit that is difficult to achieve in many plants. In addition, lead smelters produce SO2 and this must be converted to sulfuric acid. A nearby market for the acid must exist otherwise SO2 will have to be emitted in the environment, which is unacceptable. Both problems can only be solved by using a hydrometallurgical route to process the sulfide concentrate. No lead fumes will be emitted in the environment and elemental sulfur could be produced, which is easy to store or ship to sulfuric acid manufacturers.

PRESENT TECHNOLOGY The present process for lead production suffers from numerous steps, high operating cost, and excessive pollution problems (Figure 1).

Figure 1 - General scheme for the pyrometallurgy of lead

Refining Molten lead is sent for refining in kettles at controlled temperature to collect the dross, other impurities are then removed, then silver is recovered by zinc, and finally silver is recovered by cupellation while zinc is recovered by vacuum distillation (Figures 2-4).

Figure 2 - General scheme of lead refining

Figure 4 - Removal of silver Figure 3 - Refining of lead HYDROMETALLURGY OF LEAD The first review on the hydrometallurgy of lead was published in 1924 by Ralston of the US Bureau of Mines in Berkeley, California 1. He drew attention to the solubility of PbCl2 and PbSO4 in brine solutions and summarized their solubility data. The most important process that was operating on a small industrial scale using this technology was that developed by Tainton and his co-workers at Bunker Hill & Sullivan in Kellogg, Idaho (Figure 5).
O2 PbS concentrate Roasting H2 O SO2

PbSO4, impurities Leaching

Filtration CaCl2 Leaching

Impurities

Filtration Cl2 PbCl4

2-

Gangue, CaSO4

Absorption

Aq. Electrolysis

Ca(OH)2

Refining

Ag

Pb

Figure 5- Tainton process (1924)

Tainton himself never published a description of his process, but an account of it was given in 1945 by Bownan in Liddells Handbook of Nonferrous Metallurgy 2 and in 1953 by Van Arsdale in Hydrometallurgy of Base Metals 3. The process, however, was not successful and the plant was dismantled. The failure of the process seems to have been in the electrowinning step since chlorine was formed and was not disposed of properly beside its corrosion problems. In addition, lead powder obtained was not satisfactorily handled and was contaminated by silver. Intensive research on the hydrometallurgy of lead was undertaken in 1970s and 1980s when environmental problems due to lead smelters became of much concern. However, no viable process resulted. In the present review it will be shown that the production of lead by a hydrometallurgical route is certainly possible. Electrometallurgy of lead Lead may be deposited from aqueous media at high cathode efficiencies. Lead electrodeposited from aqueous solutions of the acetate and nitrate baths have no commercial application because the deposits tend to be acicular and porous hence difficult to wash. The fluoborate, fluosilicate, and sulfamate baths have achieved technical importance for commercial application because of the smoothness of the deposits. Electrodeposition of lead from fluoroborate bath was patented in 1886 by G. Leuchs in Germany [4]. The solution is prepared from basic lead carbonate and fluoroboric acid. The bath containing 100g/L Pb, 42 g/L fluoroboric acid, 10g/L boric acid, and 0.2 g/L glue operated at 15-40C. Electrowinning of lead in nitrate and fluorosilicate media yields lead metal at the cathodes and PbO2 at the anodes. Addition of small amounts of phosphate or arsenic compound in fluorosilicate system will prevent the formation of PbO2 on anodes. Impurities should be removed from solution before electrowinning. It was also proposed to precipitate lead as PbSO4 leaving impurities in solution converting it to PbCO3 by ammonium carbonate, then dissolving the carbonate in H2SiF6 for electrolysis. Ammonium sulfate generated during this process can be marketed as a fertilizer. This proposal, however, was not attractive to industry. The electrolytic refining of lead was invented in 1901 by Anson G. Betts [5]. Crude lead was cast in form of anodes and immersed in an electrolyte of lead fluorosilicate solution. The cathodes were made of pure lead. When the current was passed, pure lead deposited on the cathode while the impurities remained as slimes on the bottom of the cell. The process is used today for refining of about 20% of the lead bullion. Bullion usually contains 12-15% impurities. It is necessary to control the level of arsenic, antimony, and bismuth in the anode to maintain its integrity and slime adherence during electrorefining. Electrolysis of fused PbCl2 NaCl at 500C has been successfully operated and chlorine generated can be used in the oxidation of ferrous chloride to ferric, which is used in the leaching step, or for the direct attack of lead sulfide concentrate. Lead forms as a molten pool at the bottom of the cell [6]. BASIC CHEMISTRY The fact that PbSO4 is insoluble in water while ZnSO4 and CuSO4 are soluble suggested to early

metallurgists a method for separating these metals, which are usually occurring together in ores, by roasting at about 500C: MS S O 2 g MSO 4S followed by leaching with water. A small amount of SO2 is formed during roasting due to the presence of other sulfides, which form oxides instead of sulfates [1]. Later, it was found that slurrying the concentrate with water then heating in an autoclave at 220C:
MS S O 2 aq MSO 4S, aq

followed by filtration resulted in a solution containing all the copper and zinc sulfates while all the lead and silver sulfates remained in the residue and can be sent to the blast furnace. This was the process adopted on industrial scale in 1960s by Bunker Hill in Kellogg, Idaho (Figure 6 and Table 1) [7]. This technology was thought to be more advantageous than the roasting process because no SO2 would be evolved but in fact it was not, since SO2 was generated in the blast furnace gases due to the decomposition of lead sulfate. It had the disadvantage further that sulfate ion in solution had to be disposed of by precipitation with lime.
PbS Concentrate O2 Aq. Oxidation
H 2O

Filtration PbSO4, Ag2SO4 Blast Furnace Crude Pb Refining

CuSO4, ZnSO4

CO2, SO2

Ag

Pb
Figure 6- Processing of lead sulfide concentrates at Bunker Hill, Kellogg, Idaho (1960s). High temperature aqueous oxidation (220oC)

Further research demonstrated that there are a large number of options available to choose from for the hydrometallurgical treatment of lead sulfide concentrates without the production of SO2. The following points should be taken in consideration: Silver, zinc, and copper are usually important by-products. One should recall the following solubility data to help selecting the proper leaching system: PbCl2, AgCl, PbSO4, and Ag2SO4 are insoluble in water but soluble in concentrated brine solution. Lead fluorosilicate, PbSiF6, is soluble in water while Ag2SiF6 is not. Sulfates and chlorides of copper (II) and zinc are soluble in water. All nitrates are soluble while carbonates are not.

Galena is easily attacked by dilute acids generating H2S [8-10]: PbS + 2H+ Pb2+ + H2S which can be collected and converted by standard technology to elemental sulfur at 400C using alumina as catalyst: H2S + O2 S + H2O However, the toxicity of H2S and its explosive nature renders this route undesirable.

Galena is attacked by concentrated H2SO4 at 100C to form SO2 and elemental sulfur: PbS + 2H2SO4 PbSO4 + SO2 + S + 2H2O The reaction is simple but offers no special advantage since SO2 is generated. Table 1 Aqueous oxidation of lead sulfide concentrate at 220C (Bunker Hill Process) Feed Solution Residue % g/L %
Pb Zn Cu Fe S As Sb Bi Sn Cd Co Ni Mn In Ca Mg Insol. Ag (oz/ton) 50.6 8.7 6.46 7.8 16.4 2.2 2.0 0.006 0.07 0.15 0.025 0.40 0.14 0.08 0.2 0.15 2.3 131.7 Trace 49.5 47.8 4.0 67.6 1.36 0.15 0.0 Trace 0.85 0.13 1.78 0.06 0.0 Trace 51.2 1.20 0.83 6.7 9.4 2.0 1.8 0.006 0.06 0.02 0.01 0.11 0.10 0.04 0.2 0.10 3.0 140.1

SULFATE AND CHLORIDE SYSTEMS Aqueous oxidation of PbS in acid results in the formation of elemental sulfur [11,12]: PbS + O2 + 2H+ Pb2+ + S + H2O

When H2SO4 is used, PbSO4 will be formed and when HCl is used then PbCl2 will be formed together with an appreciable amount of PbSO4 since a portion of sulfide sulfur is oxidized to SO42- and other components of the concentrate will form soluble sulfates. There is no advantage in using the sulfate system because of the difficulties encountered in the recovery step. When Fe3+ ion is used instead of oxygen the following reaction takes place [13-16]: PbS + 2Fe3+ Pb2+ + 2Fe2+ + S Solution purification can be achieved by cementation of the impurities with lead powder. Ferrous ion can then be oxidized back to ferric for recycle. Oxidation may take place by oxygen: Fe2+ + O2 + 2H+ 2Fe3+ + H2O Or by chlorine when FeCl3 is used: 2Fe2+ + Cl2(aq) 2Fe3+ + 2ClIn this case chlorine could be obtained from the electrolysis of PbCl2 either in aqueous solution (complexed with NaCl) or in the molten state (Figure 7). This was the basis of the processes developed by researchers at US Bureau of Mines at Reno, Nevada [17-22] and others [23]. This shows again that the chloride system is more preferable than the sulfate system, since in the latter case the sulfate ion must be disposed of. Oxidation of Fe2+ may also be achieved in the electrolytic step whereby the evolution of chlorine is suppressed as proposed by French researchers [24].
PbS concentrate Fe
3+

HCl Aq. Oxidation Filtration Flotation Brine Leaching Filtration Gangue Soluble chlorides S

Fe2+ oxidation Cl2

Crystallization PbCl2 Electolysis Pb

Figure 7- Processing lead sulfide concentrates with formation of elemental sulfur. Chloride system

Other researchers added a variety of reagents during the aqueous oxidation step to solubilize PbSO4 formed. For example, ammonium acetate [25,26], ammonia [27], sodium hydroxide [28], and amines [29]. Instead of using acid and ferric ion, aqueous chlorine solutions are used [30]. In all these systems there is always formation of variable amounts of PbSO4. CARBONATE SYSTEM To avoid the formation of PbSO4 or PbCl2, aqueous oxidation of PbS was conducted by Chinese researchers 31-33 in presence of ammonium carbonate at about 50C. Lead carbonate and elemental sulfur are formed: PbS + (NH4)2CO3 + O2 + H2O PbCO3 + S + 2NH4OH Residence time about 6 hours and yield of sulfur is 60%. After flotation of elemental sulfur, PbCO3 was solubilized in fluorosilicic acid, the solution purified, then electrolyzed for electrowinning of lead (Figure 8).
PbS concentrate O2 Aq. Oxidation (NH4)2CO3

Filtration Solids Flotation H2SiF6

Recovery

S, Ag

PbCO3, gangue Dissolution

Filtration

Residue containing Ag

Purification

Impurities

Electrolysis

Pb

Figure 8 - Processing lead sulfide concentrates in carbonate system

NITRATE SYSTEM The nitrate system has the advantage that both lead and silver will go into solution and hence separation can be readily achieved. Using HNO3, however, has the disadvantage of generating nitric gases, which must be re-converted to HNO3 [34]. The use of ferric nitrate was already proposed in 1939 by Fande [35 and was studied further in 1987 by Fuerstenau et al. 36 who

showed that the following reaction takes place: PbS + 2Fe(NO3)3 Pb(NO3)2 + 2Fe(NO3)2 + S Complete dissolution of galena took place at 70C in 0.25 M Fe(NO3)3 solution at pH 1.2-1.4 in 100 minutes. Recently Pashkov and co-workers [37] demonstrated that lead could be selectively extracted from lead sulfide concentrates into solution at room temperature in less than 30 minutes using ferric nitrate. It was proposed to remove iron via ferrous nitrate oxidation and ferric nitrate self-decomposition in autoclave, yielding hematite and NO + NO2 gases; this process has been previously studied by Van Weert and co-workers [38,39]: 6Fe(NO3)2 + 5H2O 3Fe2O3 + 2NO + 10HNO3 Nitrous gases are employed to produce nitric acid and to dissolve hematite forming ferric nitrate solution for recycle: Fe2O3 + 6HNO3 2Fe(NO3)3 + 3H2O After purification of the solution from copper and bismuth by cementation on lead and the separation, if necessary, of zinc by organic solvents, lead can be recovered by electrowinning at the cathode as Pb and at the anode as PbO2 (Figure 9): Pb(NO3)2 + 2e- Pb + 2NO3Pb(NO3)2 + 2H2O + 2NO3- PbO2 + 4HNO3 + 2 eoverall reaction 2Pb(NO3)2 + 2H2O Pb + PbO2 + 4HNO3
Fe(NO3)3 PbS concentrate

Leaching

Filtration Solution NO + NO2 Regeneration Filtration HNO3 Dissolution Fe2O3 Solution Purification Heating

Flotation

Gangue

Bi, Cu, Ag, Zn

Electrolysis

Pb + PbO2

Figure 9 - Processing lead sulfide concentrates in nitrate system

This system, however, will not solve the problem of lead metallurgy because of the need to recover nitric gases to form nitric acid, the use of diaphragm cell is undesirable, and only half of the lead is recovered in the metallic state. Cementation of lead by iron from nitrate solution is not possible because of the oxidizing power of the nitrate ion and the formation of iron oxide [40]. FLUOROSILICATE SYSTEM Since lead fluorosilicate is soluble in water, it was suggested by workers at US Bureau of Mines in Rolla, Missouri 41,42 to leach lead sulfide concentrate in fluorosilicic acid: PbS + H2SiF6 + O2 PbSiF6 + S + H2O After filtration of the residue and solution purification, lead can be recovered by electrolysis. The residue contained elemental sulfur, silver, zinc, and copper (Figure 10). A recent study in this direction was published by Taylor et al. [43]. Attempts to electrowin lead from the leach solution were not successful because of low current efficiency and undesirable cathode morphology due to impurities present. To overcome this problem, the Bureau of Mines researchers suggested adding H2SO4 to precipitate PbSO4, transform the sulfate into carbonate, dissolving PbCO3 in H2SiF6, then electrolyzing the pure lead fluorosilicate solution. High purity lead was obtained but the procedure suffers from the numerous steps involved and the generation of ammonium sulfate as a by-product.
PbS concentrate H2SiF6 Leaching Solids O2

Filtration Solution Impurities Purification

Flotation

Electrolysis

Silver recovery

Figure 10 - Processing lead sulfide concentrates in fluorosilicate system

Pb

CHLORINATION The use of gaseous chlorine has the advantage over the aqueous chloride system is the absence of PbSO4 formation since all the sulfide sulfur is transformed to the elemental form. There have been early attempts in this direction at the beginning of the twentieth century but without success owing to the difficulties encountered in handling chlorine 47. About sixty years later,

researchers at the US Bureau of Mines in Rolla, Missouri re-examined this technology and recommended the recovery of lead by the electrolysis of fused PbCl2 48. A pilot plant was later operated at Hazen Research Center in Golden, Colorado based on such technology 49 (Figure 11). Chlorine gas is fed to rotating reactor counter-current to the flow of fresh concentrate so that any sulfur monochloride formed becomes the chlorinating agent: PbS + Cl2 PbCl2 + S 2S + Cl2 S2Cl2 PbS + S2Cl2 PbCl2 + 3S The temperature in the reactor is 155-175C.
PbS Cl2
concentrate

Chlorination Brine Leaching Filtration Crystallization Centrifuge PbCl2 Electrolysis Pb S + gangue Fe powder Cementation Filtration Silver recovery Solution for Cu, Zn recovery

Figure 11 Processing lead sulfide concentrate by chlorination

Lead chloride and other chlorinated compounds are then solubilized in hot brine solution. Lead chloride is then crystallized and, the anhydrous PbCl2 is fed in a fused salt cell containing 90% PbCl2 and 10% NaCl and operating at 500C. High purity lead was obtained. Mother liquor from crystallization step is treated with sponge iron to remove silver. A bleed stream is treated with NaOH or Na2CO3 to remove other impurities. Work at Universal Oil Products laboratory in Des Plaines, Illinois also confirmed this technology 50. FLUOROBORATE SYSTEM Researchers at Engitec Tehnologies in Milan, Italy found out that galena concentrates was solubilized in fluoroboric acid containing ferric fluoroborate at 80oC liberating elemental sulfur while silver, copper, bismuth, and antimony remain in the residue [44-46] (Figure 12): PbS + 2Fe(BF4)3 Pb(BF4)2 + 2Fe(BF4)2 + S

The solution is then electrolyzed in a diaphragm cell where pure compact lead is deposited at the cathode and the ferrous fluoroborate is oxidized at the anode to ferric fluoroborate for recycle: Pb2+ + 2e- Pb Fe2+ Fe3+ + ePbS concentrate
HBF4 + Fe(BF4)3

Leaching Solids

Filtration Solution
Bleed for zinc recovery

Electrolysis

Flotation

Lead

Silver recovery

Figure 12 - Processing lead sulfide concentrates in fluoroborate system

No oxygen is formed at the anode and this is a great advantage because the voltage will be lower. Air is sparged at the anodes to prevent the formation of PbO2. A typical electrolyte will have the following composition in g/L: Pb2+ 50-70, Fe2+ 25-30, Fe3+ 35-30, fluoroboric acid 35-45, total HBF4 325-335. Temperature of electrolysis 35oC, anodic and cathodic current densities 200-250 A/m2, and graphite anodes can be used. Cell voltage at 300 A/m2 is 2.10 volts, the current efficiency is 96%, and energy consumption is 570 kWh/tonne Pb cathode. Lead produced is 99.99% and the overall recovery is 96.1%. Zinc is partially solubilized in the leaching step but not electrodeposited; it can be recovered from the bleed solution. Fluoroboric acid, HBF4, is prepared industrially by reacting hydrofluoric acid with boric acid: H3BO3 + 4HF HBF4 + 3H2O The reaction is exothermic and the acid is available only as a 48% solution. Ferric fluoroborate is prepared by reacting the acid with Fe2O3. Fluoroboric acid is more expensive than fluorosilicic acid but it has the advantage of being more stable on heating and its solutions have higher electrical conductivity. Fluoroboric acid was used for more than fifty year by Norddeutsche Affinerie in Germany for refining lead bullion with high bismuth content. Presently it is used in electrodeposition of lead and its alloys, especially in printed circuit board manufacture. Doe Run Company [former St. Joe Lead] had a demonstration plant in southeast Missouri, running for more than 3 years. Now it is in stand-by. (Figures 13 and 14). It is operating the cell at 8000 A/m2 with an efficiency of 80 85 % and a current consumption between 900 and 1000 kWh/t of lead, and lead recovery is about 99 %. In the same location in Missouri there is a small unit (50 kg/d) that is available for testing. It is expected to invest more than $150 million.

Figure 13 - Doe Run pilot plant in Missouri for electrolysis of lead in fluoroborate system

Figure 14 - Doe Run pilot plant in Missouri for electrolysis of lead in fluoroborate system

CONCLUSIONS There have been many hydrometallurgical methods proposed for treating lead sulfide concentrates. It seems that the best method is by leaching in fluoroboric acid containing ferric fluoroborate at 80oC liberating elemental sulfur while silver remains in the residue. The solution is then electrolyzed in a diaphragm cell where pure compact lead is deposited at the cathode and the ferrous fluoroborate is oxidized at the anode to ferric fluoroborate for recycle. Any silver present in the concentrate can then be recovered from the residue after flotation of elemental sulfur. The recent work by Asarco engineers [51] based on granulating the lead bullion obtained by smelting, leaching the granules in ferric fluoroborate, purification of solution, then electrowinning using a diaphragm cell is not justified because pollution problems during

smelting have not been solved (Figure 15). The problem of lead metallurgy should be attacked from the very beginning, starting from the concentrate.
Pb concentrate Smelting Bullion Granulation Fe(BF4)3 Leaching Purification Electrowinning Pb Figure 15 Schematic diagram for the proposed process by Asarco engineers [51] based on granulating the lead bullion obtained by smelting, leaching the granules in ferric fluoroborate, purification of solution, then electrowinning using a diaphragm cell Impurities SO2

Zinc had a similar history like lead up to 1980s. It was produced exclusively by roasting the sulfide concentrate to form zinc oxide, thermal reduction of the oxide, then refining the crude metal by vacuum distillation. During World War I, leaching of the oxide and electrowinning of zinc from the purified solution replaced the reduction and vacuum distillation steps. In 1980, the total hydrometallurgical route, i.e., aqueous oxidation of the sulfide concentrate to get zinc sulfate solution and elemental sulfur was introduced on industrial scale. Copper had also a similar history until at the beginning of the twenty first century when the aqueous oxidation of copper sulfide concentrates was also introduced on industrial scale by Phelps-Dodge in Arizona. Will lead follow a similar situation? The present writer is convinced that the answer is yes.

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