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Physical properties

Property Value
Symbol Pb
Atomic number 82
Standard Atomic weight 207.2
Electronic configuration [Xe]
Crystal structure FCC
Density at 20⁰C 11.34g/cm
Melting point 327°C
Boiling point 1755°C
Coefficient of thermal 29.1 μm/m•°C
expansion
Thermal conductivity 34.9 W/mK
Elastic modulus 16.8 GPa
Poisson ratio 0.42
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 Introduction

 Growth in transportation field, principally in conventional internal combustion

engine automobiles, has been the main factor in sustaining moderest growth in lead
consumption of around 2.4% in 1998

History
 The use of lead goes back as far as 5000 B.C from ancient Egyptians and also
included weight standards, coinage, sheathing, lining , trinkets, anchoring of iron
rods and making of seals.

 Romans used lead extensively for water piping. Latin name “Plumbum” for lead
came from the word for water spout, and from it has come the name Plumber

 In the twentieth century the appearance of automobile , chemical and machine

industries created large new uses for lead in gasoline antiknock additives , bearings
and plumbing alloys, accumulator batteries and chemical equipment. Modern use
include glass making, sound attentuation and radiation shielding

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 Important ores

Name of the ore Chemical composition % of the metal

Galena or lead sulphide PbS 86

Cerrusite or white lead ore PbCO 3 77.5

Anglesite PbSO 4 68.3

Pyromorphite Pb 5(PO 4) 3Cl 76

Wulfenite or yellow lead PbMoO 4 56

ore

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 Major industries

Gravita India Ltd is the major producer of lead in India

NSAIL produces lead and its various alloys
HZL – Major producer of lead in Bihar( Tundoo)

85% lead deposits occur in Rajasthan in India. The important lead deposits in india
include Rampura-Agucha, Rajpura-Dariba, Sindeshwar, and Zawar.

Uses of lead

Manufacture of batteries, cable, pigment, flexible sheet and pipe. Basic Pb carbonate
such as 2PbCO 3.Pb(OH) 2 used in Pb pigment from on basis of grade point. Also,
litharge (PbO) used in reverberatory furnace for oxidation for pigmented varnish and
glass production.

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Production of lead by Pyrometallurgical method

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 Production of lead from sulphidic ore

 Lead ores contain many other impurities which are to be beneficated and they mainly
include crushing, dense medium separation, grinding, froth flotation and drying of
concentrate. Lead flotation is primary stage in lead-zinc and lead-zinc copper ores.
 The main process is the sinter oxidation-blast furnace reduction route. In this process
the lead ore is sintered in presence of oxygen to make it free from sulphur. The
resultant product is reduced to metal lead bullion with minor impurities in blast
furnace with reducing agent which can be further refined.

 Modern sintering technique combines roasting with agglomeration of charge in the

sintering step. Sintering is carried out in continuous sintering machine called
DWIGHT AND LLYOD. Updraft sintering is preferred because of higher capacity,
elimination of precipitate wind box, Production of high grade SO 2 gas

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 The Pb-S-O system

 Lead in sinter occurs mainly as lead monoxide or lead silicate. Oxidation starts with
the formation of stable reaction product at the oxygen and sulphur dioxide partial
pressures and temperatures commonly used in sintering. Lead sulphate then reacts with
lead sulphide, decomposing to increasingly basic sulphates and ultimately to lead
monoxide

 The temperature of the sinter charge

must be high enough to attain the area
of PbO predominance i.e.,>950C

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 Oxidation starts with formation of lead sulfate, which is stable reaction product at
oxygen and sulfur dioxide partial pressures and temperatures commonly used in
sintering. Lead sulphate then reacts further with lead sulfide, decomposing to
increasingly basic sulfates and ultimately to lead monoxide.

 This processes are categorised as excess sulphur or excess oxygen, depending on

whether the reaction series exhausts the oxide and sulphate or sulphide species, rsp.
In this %S reduces from 16-18% to 1-2%

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 Blast furnace reduction of sinter product

 The second part of roast reduction process blast furnace reduction, where the lead
content of sinter (mainly lead oxide)is reduced to metallic lead, other metals such as
copper, antimony, arsenic and noble metals are also produced. Other constituents are
carried out as silica slag.
 The charge to blast furnace comprises Sinter, which incorporates the roasted
concentrate and fluxes. Other oxygen-containing lead materials such as oxides and
silicates Metallurgical lump coke as the reducing and heating fuel

 The lead blast furnace is a counter current reactor in which a charge (sinter and coke)
moves through a vertical shaft in countercurrent to the ascending gas flow. The
descending charge successfully passes through the preheating zone, the reduction
zone, the melting zone, and finally the combustion zone. The liquid reaction products
collects in the furnace crucible, which is located below the tuyere.
 In the combustion zone, atmospheric oxygen blown in through the tuyeres reacts
with coke to form carbon dioxide with extensive release of heat which further form
carbon monoxide by ascending through coke rich layer. In the melting and reduction
zone heat is transferred from the gas and liquid slag is formed from fluxes and sinter
gangue.
 For optimal heat and mass transport in reaction zone, gas velocity should be high and
the resistance to gas flow low
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 The exothermic reaction of lead oxide by carbon, CO and H begins at low temp. more
intense temp. are required for other oxygen containing lead species(aluminates, silicates
and ferrites)
 PbO also helps in reducing PbS left unroasted in the sinter machine and hence combine
with silica( SiO 2) in the charge to form 2FeO.SiO 2. Hence the lower melting point of
slag and increase the fluidity of metal layer.
PbSiO 3+Fe →FeSiO₃+Pb
PbO+Fe→FeO+Pb
 The noble metals are dissolved in lead product
(bullion. The copper content of sinter is
captured in the form of matte in sulphide
form. However if sulphur content in matte is
low than copper in the form of oxide or
sulphide is incorporated into slag to avoid
copper going back into slag.

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 Products of lead blast furnace
1. Slag layer
2. Matte layer
3. Speiss layer
4. Lead bullion/base bullion

 Speiss is formed when the burden contains of arsenic, nickel, cobalt and antimony
in large amounts that they can’t be taken by matte. It is undesirable

 Lead bullion must be refined further to obtain pure lead

 Matte- a sulphidic product of blast furnace smelting, forms only if burden contains
enough sulphur. It can be avoided if charge does not contain too much copper.
 Slag- contain large amounts of zinc which must be further processed.

Flue dust and Bag house dust contains fumes and dust particles are carried away by top
gases. Top gases usually contain 3-4% carbon monoxide which represent unavoidable
energy loss

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 Direct smelting reduction processes

 The fundamental problems encountered in the sinter, oxidation-blast furnace method of

lead production (e.g., high process and hygiene ventilation gas volumes , high
maintenance cost for machinery and expensive coke fuel for reduction) gave a quest for
more simpler way of lead production by direct smelting processes
 In case of direct smelting of a very high grade lead concentrate, upto 80% of lead in
charge can be obtained as direct bullion with the remaining 20%as a slag rich in lead
monoxide. With low grade feed charges requiring auxiliary fuel, all lead can be
oxidized to a high lead slag with no direct bullion production.

 The second step is reduction of lead from high grade slag (25-40%Pb). Slag has been
reduced by submerged fuel combustion or injection , reduction assisted by an electric
furnace and a combination of these techniques.

Two important types of direct smelting processes

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a.Air flash smelting process- Boliden process

 Dry high grade galena concentrate(65-75% Pb) is blown into an electric furnace with
oxygen enriched air. Lime stone flux and coke breeze are also included in the feed
charge . Suspended lead sulphide particles react to produce lead monoxide and lead
metal , which collect in the furnace hearth along with the fused slags constituents.
Desulphurisation is not complete . The furnace products are 2-3% sulphur, slag
containing 4-5% Pb and flue dust. Desulphurisation of bullion is completed by air
blowing in down stream converter. Product slag is treated in a slag fuming furnace
along with copper slag for zinc and lead recovery.

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 b.Oxygen flash smelting

 In all oxygen flash smelting processes, very complete desulphurization of charge

is effected through the production of strongly oxidizing slag. The required oxygen
potential can only be achieved with lead monoxide when its weight fraction is high
(>35% lead in initial slag).
1. Kivcet process
2. Boliden kaldo process
3. Outukumpu process

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 Kivcet process

 The oxidation section of the electric furnace freeboard is separated from the reduction
section by a water cooled, gas tight wall (d) which dips into the furnace slag bath. Dried
and blended charge components consisting of lead concentrate and other lead bearing
materials, required fluxes, recycle flue dust, and oxygen are fed through burners (a) at
top of the oxidation shaft(b). Combustion of charge constituents at temperature upto
1400c and a shaft height of 3-5 m permits almost complete desulphurization before
collection of reaction products in the slag

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 Reduction of PbO is done by a layer of coke particles floating on the slag bath under
the combustion shaft . Reduced slag and lead bullion flow under submerged partition
wall (d) into reduction section and slag composition 2-3%lead .

 Lead bullion is removed from the furnace by syphon and slag is withdrawn
continuously from weir overflow. Sulphur dioxide gas flue dust mixture is cooled by
vertical stack boiler

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 Boliden-kaldo process

 It employs a top blown rotary converter in a batch manner. A cycle starts with oxygen
combustion of dry charge constituents into a preheated empty vessel. Charge
combustion is continued until lead bullion and high lead slag have accumulated to the
limit of the vessel or volume capacity. Charge combustion is stopped and slag reduction
starts. Lead sulphide concentrate is used to reduce a major portion of PbO in slag
followed by coke breeze reduction to discharge slag composition . The vessel slag and
bullion contents are then poured into ladles, and smelting cycle repeated. It can handle a
variety of lead containing charge materials.

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 Outokumpu process

 It is standard world wide pioneered by Outokumpu Oy of Finland in late 1940’s.

 Lead concentrate and flux are dried in a rotary dryer(a), mixed with recycle flue dust,
and then flash smelted with oxygen in the oxidation furnace smelting shaft(b). High
lead slag and lead bullion collected in the furnace may be tapped separately to
provide a direct lead bullion product. Alternatively, if direct lead bullion production is
small, slag and bullion are tapped together into a separate electirc furnace(d). In the
electric furnace, pulverised coal is injected with nitrogen into slag bath to reduce
monoxide

 Bullion and slag are continuously

tapped to electric furnace for slag
reduction

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Oxygen- Slag Bath Smelting,QSL process

 The QSL process is named after its inventors P.E QUENEAU and R. SCHUHMANN
Jr., as well as the process developers Lurgi Chemie.
 Lead concentrate, fluxes, auxiliary coal fuel, recycle flue dust, and other charge
Components are blended(b) in a moist condition to form a single feed charge to QSL
reactor. The reaction vessel is a horizontle refractory lined cylinder that is divided by a
partition wall into an oxidation section (c) and a slag reduction section (d). Nitrogen-
shrouded tuyeres on bottom of reactor injected oxygen into oxidation section. Similar
shrouded tuyeres were employed for submerged combustion of oxygen-coal or
oxygen-natural gas reduction mixture. Blended feed was charged through ports at the
top of oxidation reaction section into injection injection-agitated lead and slag bath

 Slag from the oxidation zone flows through an underflow port in vessel partition wall
into slag reduction zone(d). Lead bullion is removed by a lead syphon at the side of
vessel. The smelting vessel is rotated by 90 degrees during stoppages to bring the
injection tuyere systems above the vessel slag level.

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 Refining of lead bullion

 Production lead, known as bullion contains numerous dissolved impurities. Molten

lead is an excellent solvent for a variety of metals and compounds and raw bullion
commonly contains copper, iron, zinc, sulfur, arsenic, tin, antimony, bismuth, noble
metals oxygen, and occasionally nickel, cobalt and tellurium. The lead content varies
between about 90 and 99.9% depending on process and feed quality.

 Pyrometallurgical refining
 Electrolytic refining

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 Pyrometallurgical refining

 This process is generally operated in batch manner, but process steps involve
continuous operation. Impurities dissolved in the parent metal are enriched in a phase
that is insoluble in parent metal. It consist of:

 Liquation: Refining technique for removing impurities from base metal on the
factor such as difference in melting point of alloy components. So as a number of
layers formed on the basis of their difference in density. The crude zinc containing of
5%Pb refined in a reverberatory furnace by slowly cooling of molten matte.
 Drossing: It is a combine process of liquation and oxidation in reverberatory
furnace at around temperature 350⁰C at which many metals oxidized and skimmed off
subsequently increase to (500-550⁰)C. At that temperature Cu get eliminates using S in
the form of Cu 2S and at last softener slag( Sb,Sn,As,Te,Se) are removed.
 Removal of copper : is a two stage operation. The first is primary decoppering
by drossing (precipitation). The second is selective sulfidizing of copper , which
involves addition of sulphur.
 Desilverising:PARKE’S PROCESS- The process of desilverising Pb by addition
of Zn followed by cooling for Ag recovery .In this process Zn is added in molten Pb
because of high affinity of Zn for Ag than Pb. Two layers of Zn and Pb are formed of
which Zn solidifies first as it as higher melting point.

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 Dezincing: As Cl2 reacting with Zn to give ZnCl2 in an enclosed chamber cause
left of Pb and falling on bath looks grayish scum surface (layer of bubble formation)
which gets skimmed off.
At the end point, all Zn chlorinated and white crystal of PbCl2
appeared on surface. Vacuum dezincing desilverised lead pump to kette i. e. bath
enclosed by steel ball shaped with a stirrer and vacuum pump attached. As temperature
rose to 5400C vacuum distillation carried out in reduction of Zn content from 0.6 to
0.002% in lead.

 Debismuthizing: The base bullion consist high Bi% which get separated by
addition of Ca and Mg to forms an insoluble intermetallic compound of Bi.

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 Electrolytic refining

 The anodes is the base bullion it is casted , forged or rolled are placed into an
aqueous solution of 9% Pb as Pb2SiF6 and 8% H2SiF6 as electrolyte.
 Cathodes are thin rolled sheets of highly pure lead. A potential of only 0.2–0.4 volts
is required for the process to commence.
 Reaction takes place, when electricity passed and impurities are removed. They
form as a slag and the by products are formed as anode slime at the bottom of it.
 Lead (II) ions migrate through the electrolyte to the cathode
 The electrolyte has advantages like it is stable and hardly contaminated during
electrolysis and can dissolve impurities in base bullion
 This produces purer lead than that obtained by furnace refining.
 Reactions :
At the anode: Pb(s) → Pb2+(aq) + 2e–
At the cathode: Pb2+(aq) + 2e– → Pb(s)
 During the process the temperature is at 35-40 degree Celsius with initial voltage
of 0.5V

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