Galena (PbS)

Brief Overview of Lead Ores

• Primary Lead Sulfide ore (87% lead)
• Chemical Structure- PbS [Lead (II) Sulfide]
Galena • Contains traces of zinc, silver, iron, arsenic, selenium

• Secondary Lead sulfide ore and an oxidized form of Galena

• Chemical Structure- PbSO4
Anglesite • Contains almost 74% Lead

• Also known as white lead ore, occurrence with anglesite

• Chemical formula – PbCO3 (Lead carbonate)
Cerussite • Formed by reaction of Galena with carbonated water.
✓ Lead extracted from mined ores
✓ Over 60 ores containing lead are mined worldwide
✓ Only 3 lead ores are commercially viable
✓ 3 million MTs of annual lead production worldwide from ores, (roughly 50%)

• Lead is usually smelted in a blast furnace using the carbon from the sintering machine to provide the heat source.
• As melting occurs, several layers form in the furnace. The molten lead layer sinks to the bottom of the furnace.
• A layer of the lightest elements, including arsenic and antimony, floats to the top and is referred to as the "speiss." A
"matte" layer also forms from the copper and metal sulfides. Finally, a layer of blast furnace slag, which contains
mostly silicates, also forms.
• The lead from the blast furnace, called lead bullion, then undergoes the drossing process.
• The bullion is agitated in kettles then cooled to 700-800 degrees. This process results in molten lead and dross. Dross
refers to the lead oxides, copper, antimony and other elements that float to the top of the lead. Dross is usually
skimmed off and sent to a dross furnace to recover the non-lead components which are sold to other metal
manufactures.
• Finally, the molten lead is refined.
• Pyrometallurgical methods are usually used to remove the remaining non-lead components of the mixture. The non-
lead metals are usually sold to other metal processing plants. The refined lead may be made into alloys or directly cast.
✓ Vapour pressures of lead sulphide, lead oxide and lead metal
are all high at the temperatures used in the smelting of lead
concentrates.
✓ Even low levels of lead in blood cause health problems and
exposure to lead sources should be minimized
✓ The predominant technology for the past century for the
oxidation and agglomeration of lead sulphides has been
updraft sintering process; flexible in the range of materials but
poses inherent risks through the release of fine particulate
lead.
✓ Principally bath smelting processes that enable the process
gases to be confined, captured and safely treated.
✓ Although single step or direct smelting process to lead metal is
thermodynamically possible at high temperature, more
commonly, a two-step process is employed in which the
concentrates are fully oxidized forming high lead oxide slags;
the lead oxide is subsequently reduced to metal from the
molten slag.
 Lead secondary extraction (From Batteries)

Even at low levels, lead damages the intellectual development of young children, reducing IQ and attention span.
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 INTRODUCTION

• Globally, over 50% of the lead used annually comes from recycled sources
• Production from recycling is also termed as secondary Lead Production
• Basic processes involved: Scrap pre-treatment, Smelting and refining
• Alternative approaches include electrolysis and leaching of lead scrap after the pre-treatment

Scrap Pre-treatment
• Scrap batteries are drained, crushed and separated in 4 fractions
• Plastic, Rubber, Metallic lead, and Sludge
• Lead plates, posts, and intercell connectors are collected and piled up.
• This lead scrap is then put in rotary furnace or reverberatory to separate from metals with higher melting points.
• This partially purified lead is fed to smelter for further operations

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Lead paste is mixture of PbSO4,
PbO, PbO2, Pb2O3 and Pb

Lead is a highly poisonous material affecting almost every organ in the body, with the nervous system the most seriously
affected by the toxicity of lead, in both children and adults. Long-term exposure can result in decreased cognitive
performance in tests that measure functions of the nervous system. This can lead to behavioural problems, a learning deficit
and lower IQ 218
 ✓ the lead–acid battery components are recycled by a simple process. First, the
battery case is broken open, and the sulfuric acid electrolyte is drained out and
collected.
✓ The plates and connectors can be removed from the case at this point and
recovered whole. Alternatively, the drained battery can be sent to a hammer-mill
for size reduction, and the plastic and lead can be separated by a simple sink-
float device.
✓ The recovered lead (a low-melting metal) is remelted and purified to make new
battery components.
✓ The plastic is melted and molded into new cases. The acid can be neutralized or
processed to sulfate salts for various uses, such as the manufacture of soap.

✓ Smelting has a Global warming potential of ~0.55 kg CO2/ (kg Pb)

✓ In addition to the release of CO2 from oxidation of coke, there are other
highly toxic emissions from the smelting process termed metal
hazardous air pollutants (HAPs).
✓ Metal HAPs are predominantly composed of compounds of lead,
antimony, arsenic and a small amount of other metal compounds.
The Extraction of Lead from Its Ores by the Iron-Reduction Process: A Historical Perspective

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 SMELTING
• Smelting produces lead by melting and separating the
lead from metal and nonmetallic contaminants and by
reducing oxides to elemental lead.
• Pre-treated scrap lead, rerun slag, scrap iron, coke,
recycled dross, flue dust, and limestone are used as
charge materials to the furnace.
• Heat generated by reaction of the charged coke with
blast air is blown into the furnace.
• Pressure of 3.4 to 5.2 kPa with an exhaust temperature
650 to 730°C is maintained.
• As the lead charge melts, limestone and iron float to the
top of the molten bath and form a flux that retards
oxidation of the product lead.

Ref: https://www3.epa.gov/ttnchie1/old/ap42/ch12/s11/final/c12s11_1995.pdf
 REFINING
• Refining involves softening, alloying and oxidation of crude
lead.
• kettle type furnaces are used.
• Refining and alloying temperatures are in range of 300-700oC.
• Alloying furnaces melt and mix ingots of lead and alloy
materials based on desired applications.
• Refining furnaces are used to either remove copper and
antimony for soft lead production, or to remove As, Cu, Ni for
hard lead production
• Dry drossing done to reduce lead oxide to elemental lead by
adding sawdust (source of carbon as reducing agent).
• Kettle or reverberatory oxidizing furnaces are used to oxidize
lead

Ref: https://www3.epa.gov/ttnchie1/old/ap42/ch12/s11/final/c12s11_1995.pdf
 Alternative Approach 1- ELECTROREFINING

• After Pre-treatment, molten lead scrap is cast into Anodes and cathode (right)
anodes and elemental lead recovered by for electrorefining
electrolysis
• T-shaped anodes are prepared by melting lead
scrap at 450oC and pouring into steel or carbon
mould.
• The anodes placed in electrorefining cells
containing H2SiF6 and PbO as electrolyte
• The cathodes are constituted of corroding grade
thick lead sheets for electrorefining as well as
electrowinning.
• Current of 20A, current density of 170 to 180 A/m2
and voltage 0.3 to 10V is maintained in
electrorefining cell during electrolysis

Ref: https://www.911metallurgist.com/how-to-recover-lead-from-scrap-battery/#Electrowinning 223

 Alternative Approach 2 – Acid Leaching

• The lead sludge consists of PbSO4, PbO2, traces of metallic lead and moisture
• Initially, it is leached with (NH4)2CO3 to obtain PbCO3 from PbSO4 which is soluble in H2SiF6
• Unreacted PbO2 is leached with (NH4)2CO3 and NH4HSO3 to obtain PbCO3
• PbCO3 mixed with H2SiF6 to obtain PbSiF6 (99 % lead).
• PbSiF6 transferred to electrowinning cell.

Chemical Reactions during Acid Leaching

• PbSO4 + (NH4)2CO3 → PbCO3↓ + (NH4)2SO4
• PbO2 + NH4HSO3 + (NH4)2CO3 → PbCO3↓ + (NH4)2SO4 + NH4OH
• PbCO3 + H2SiF6 → PbSiF6 + CO2

Ref: https://www.911metallurgist.com/how-to-recover-lead-from-scrap-battery/#Electrowinning 224

 ELECTROWINNING

• Electrowinning cell consists of PbO2-Ti

anodes and corroding grade lead cathode.
• PbSiF6 is continuously pumped into the cell
along with H2SiF6.
• About 99.99% pure lead deposits on the
cathode.
• Current density may be maintained upto 300
A/m2.
• Other parameters are similar as that of
electrorefining setup.

Ref: https://www.911metallurgist.com/how-to-recover-lead-from-scrap-battery/#Electrowinning 225

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