Extraction of Lead

Lecture Notes : HMETE 323

• Galena PbS
• Cerrusite PbCO3
• Anglesite PbSO4
• Lead ochre PbO
• lead occurs in nature predominantly as lead sulphide or
galena (PbS), which is its sole primary source
• galena occurs together with other minerals, particularly of
zinc
• as a result, the production of lead is closely related to that of
zinc
• lead ores contain various impurities such as silver, copper,
gold, antimony, tin, arsenic, and bismuth.
• due to its economic value, silver is a major by-product of the
lead production and accounts for 70% of world wide
production
• lead typically contain 3-10%Pb, which is in most cases
upgraded by froth flotation to 60-80%Pb
Lead Production
• predominantly produced by the smelting of lead sulfide
concentrates through the sinter plant–blast furnace route
• this route contributed to 70% of the total world primary
smelting capacity
• Technology now un-attractive due to high capital and
operating costs, as well as environmental and technical
issues
• alternate smelting processes based on the direct smelting
reduction of sulphide concentrates have emerged
• these processes integrate the oxidation and reduction
stages in a single unit, making use of exothermic heat of
sulphide oxidation
• alternate direct smelting processes involve sulphide
oxidation by either suspension (flash) smelting
• or bath smelting with subsequent reduction of a slag rich in
lead oxide
• another alternative route is the Imperial Smelting Process
(ISP) produces zinc and lead simultaneously with a
minimum energy requirement per ton of molten lead
produced
• Pb smelting is either by the sintering-reduction route or by
direct smelting reduction processes
• lead extraction exhibits one of the lowest energy
requirements per ton of metal
• lead bullion must undergo pyrometallurgical refining in
which the various metal impurities collected in the bullion
such as silver, gold, and bismuth are recovered or removed
Principles of Pb Production
Ellingham Diagram
• shows the variation of the standard Gibbs free energy of
formation, ∆G, with temperature (T) for selected oxides
∆G = ∆H -T ∆S
• to compare the relative stabilities of the various oxides, it is
prepared for oxidation reactions involving one mole of oxygen
• for the oxidation of a metal, ∆G represents the chemical affinity
of the metal for oxygen.
• when the magnitude of ∆G is negative, the oxide phase is stable
over the metal and oxygen gas
• furthermore, the more negative the value, the more stable the
oxide is
• the Ellingham diagram also indicates which element will reduce
which metal oxide.
Ellingham for selected oxides
• an Ellingham diagram for oxides illustrates the conditions at
which lead monoxide (PbO) can be reduced by either
carbon or carbon monoxide
• these reactions are representative of the reduction stage in
both the sintering-reduction and the direct smelting-
reduction processes
Ellingham diagram for sulphides (per 1/2S2gas).
• as can be seen, oxygen is the only compound that can
economically remove sulphur from sulphides
• consequently, the first step in the extraction of metals from
their sulphides involves oxidation to form SO2 and SO3,
depending on the operating temperature.
Predominance Area Diagrams (Phase Stability Phase
Diagram)
• an Ellingham diagram is one of the simplest graphical
representations of the thermodynamic data relevant to metal
production
• for a reaction system of three components, the thermodynamic
information is commonly presented in the form of predominance-
area diagrams
• these diagrams facilitate the identification of a stable phase as a
function of temperature and partial pressures of the participating
gases
• there are two main types of predominance-area diagrams:
– constant temperature, and
– variable temperature
• the chemical equilibrium related to the extraction of lead from its
sulphide (galena) is that of the lead–sulphur–oxygen (Pb–S–O)
system
 Predominance-area diagram for the system Pb–S–O at 1100 K
(827)
Variable temperature predominance-area diagram for the
Pb–S–O system at 101.3 kPa (1 atm) SO2 pressure
• lead sulphate and oxysulphates are stable at this temperature
under most roasting conditions
• temperature must be sufficiently high (>1373 K) to avoid the
formation of the oxysulphates
• the formation of metallic lead requires lower oxygen
potentials than the formation of lead oxide.
Relevant chemical & phase equilibrium
• metal & slag (molten) are produced as a result of the high
operating temperatures
• Species participating in the reactions exhibit a certain degree
of solubility in both molten phases
• S presents a significant solubility in molten lead; PbO also
dissolves in molten slag
2PbO (slag) + [S] in molten Pb = 2Pb (l) + SO2
• Equilibrium constant is given by
• low S content in the molten Pb can only be obtained
at the expense of high lead content in the slag
• thus direct oxidation of lead sulphide to metallic lead
has always been difficult
• exception is smelting of high grade lead concentrates
where metallic lead is produced by roast reactions
PbS + 2PbO = 3Pb (l) + SO2
PbS + PbSO4 = 2Pb (l) + 2SO2
• therefore lead mostly produced in 2 stages; removal
of S, followed by reduction of PbO by carbon or CO
Lead Production
• Pb can be extracted from sulphide ores (galena) by:
– oxidation-reduction route (blast furnace; ISP)
– direct oxidation to metal (by the roast reactions
KIVCET & Outokumpu-flash smelting or QSL &
Isasmelt/Ausmelt –bath smelting
Oxidation-Reduction Process
Typical Flow-sheet including refining of Pb Bullion
• PbS is oxidised in the solid state to remove sulphur to
produce PbO
• this is done in a sinter plant, with the sinter product
being reduced to Pb in a blast furnace using coke
• flux (limestone) is also added to form a molten slag
• mostly widely used path for the production of lead
bullion
• Main problems associated with this route:
– Emissions of particulate lead and greenhouse gases
– Little use of exothermic heat of oxidation during sintering
– Use of metallurgical coke
Sinter Plant-Blast furnace
• mostly widely used method for lead bullion
• accounts for 70% of total primary smelting capacity
Sinter Process
• two objectives: remove S, & produce porous product
with enough strength
• Performed in Dwight-Lloyd sinter machine which can
either be updraught or downdraught
• Drawbacks of downdraught for PbS sintering
– Off-gas stream low is SO2 content (1-2% vol.)
– Suction compresses the bed against grate, reducing its
permeability
– Molten Pb formed by roast reactions causes blockages &
corrosion problems
Dwight-Llyod Machine
• initially 30mm layer of charge is introduced and ignited
by oil/gas burner
• upon ignition, main charge is introduced with a thickness
of 300-400mm on the surface of ignited layer
• flame front then formed by blowing process air upward
• max temperatures that can be reached are ~1200 oC
• offgas contain 4-6% SO2, sinter product contains oxides,
sulphates, sulphides, some metallic Pb together with
ferrites and silicates
• Sinter product (40-52%Pb & 1-2%S)
Blast Furnace Plant
Direct Smelting
• both oxidation and reduction steps takes place in a
single step
• allows the heat of oxidation to be used directly in the
process (i.e. melting the charge)
• takes place at sufficiently high temperature (>1200oC)
to melt the oxidation products
• basis of modern lead smelting technologies such as
the KIVCET, QSL and Isasmelt/Ausmelt
• based on the roast reactions
• PbS is partially oxidised by air to produce metallic Pb,
PbO and PbSO4 which collect at the furnace bottom
forming a molten slag layer at top of liquid Pb
• desulphurization in the molten bath continues by the
roast reactions
• Lead oxide and lead sulphate react with remaining
lead sulphide to form metallic lead
• this route requires high grade lead concentrates and
produces a small amount of slag that contains a high
level of PbO which must be treated by reduction with
to recover the Pb
• Direct smelting processes offer several significant
advantages:
– minimise environmental pollution due to less creation of
dust
– considerable fuel saving due to effective utilization of heat
during the smelting operation
– higher concentration sulphur dioxide off-gas is ore suitable
for sulphuric acid manufacturing
• however, the major difficulty in all direct smelting
processes lies in obtaining both a lead bullion with an
acceptably low sulphur content and a slag with a
sufficiently low lead content for safe disposal
• in several cases further treatment of either the crude
bullion or the slag (or both) is required in a separate
operation
KIVCET Process
Pb Smelting Chemical Reactions
Secondary Pb Production
• mainly produced by recycling of waste lead acid
batteries and amounts to about 75% of total lead
produced
• battery scrap from automobile sector accounts for 80%
of old scrap recycled as secondary lead raw material
• can be processed by primary smelters or by secondary
smelters using rotary and reverberatory furnaces
• recycled batteries are first separated into metals (Pb),
plastics, waste battery acids, and a paste containing
lead sulphate (PbSO4) and oxides (PbO and PbO2)
• paste reduced by carbon to metallic Pb
• a standard lead acid battery for starting, lighting, and
ignition of vehicles has the following:
• average composition by weight
– Lead metal : 34%
– Electrolyte (free sulphuric acid) : 11-12%
– Lead oxide paste : 39%
– Others (ebonite, PVC, paper etc) : 8 -10%
– Polypropylene : 5 - 6%
Typical secondary lead production flow-sheet
Typical Slags used
• most slags used are based on CaO-FeO-SiO 2 system

Process Composition (wt%)

CaO FeO SiO2

Blast Furnace 16 30 22

KIVCET 23 26 25

QSL 22 27 22

ISP 19 42 20
Refining of Pb Bullion
• Molten lead is great solvent for metals mainly due to
its low melting point (~335oC)
• minor elements such as Ag,Cu, Au, As, Sb, Sn, and
bismuth dissolve in the produced lead bullion
• Ag is in fact a major by product of primary lead
production
• most of these minor elements are detrimental to the
properties of Pb metal, therefore must be removed
• for Sb makes Pb extremely hard
• therefore Pb bullion must be subjected to a refining
process
Typical flow-sheet for Pb refining
Imperial Smelting Furnace
• currently about 8 -10% of the world's primary - zinc
production are through the Imperial Smelting Process.
• The process co-produces lead bullion in addition to zinc
metal using a mixure of lead and zinc concentrates or
complex lead-zinc concentrates as raw material
• the ZnO and PbO sinter mix is charged with preheated coke
and lime stone in to ISF which provide simultaneous
reduction of both PbO-ZnO mixture
• the liquid lead bullion is collected at the hearth of the
furnace and zinc vapour is rapidly condensed at the top by
spraying liquid lead at 600°C
• due to the solubility difference between the two molten
• metals with gradual cooling up to 400°C, zinc metal
separate out from lead.
Imperial Smelting Furnace
ZINC PRODUCTION