Department of Materials Science and Engineering

Principles of Extractive Metallurgy– MSE4201

? ?
Mineral Ores Metal powders Metal Products

Dr. Temesgen D. Desissa (Ph.D.)

1
ASTU, MSE
Contents

• Introduction
• Reactor Design and Reaction Kinetics
• Reduction of Metal Oxides and Phase Separation
• Fuel and Ore Preparation
• Volatile Metals
• Slags and Refractories
• Matte Smelting
• Refining Processes
• Rare and Reactive Metals, Ferroalloys
• Hydrometallurgy and Electrometallurgy

2
Pre-requisites Fundamentals of Metallurgy
Semester 4 Year 1st
th

Status of Course Major Mandatory

Teaching and Learning Lecture, discussion, homework, tutorial, project, and online
Methods learning resources are also employed.
Assessment/ - Continuous Assessment (Quiz , Test, Assignments): 30 %
Evaluation & Grading - Mid-Term Exam: 20%
System - Final Exam: 40%
- Class Activity and Attendance: 10%

Reference books and materials

3
 1.Introduction

Gold ore

improving
economic value
by removing the
gangue minerals
Industrial Minerals Iron metal 4
 1.Introduction
Minerals:
• The naturally occurring chemical substances in the earth’s crust which are obtained by
mining are known as minerals

• Metals may or may not be extracted profitably from them

Ores:
• The rocky materials which contain sufficient quantity of mineral so that the metal can be
extracted profitably or economically are known as ores.

Gangue:
• The earthy or undesirable materials present in ore are known as gangue.

Metallurgy:
• The entire scientific and technological process used for isolation of the metal from its ores
is known as metallurgy.
5
1.Introduction

6
Mineral Maps of the World

7
8
9
Commercial production of metals depends on:

10
11
12
13
Aluminum
14
15
Unit operations

Unit
processes

16
LD = Linz and Donawitz

17
Zinc extraction process and
zinc slag formation

Zinc ores are:

• sphalerite (ZnS),
• zincite (ZnO),
• franklinite [ZnO(Fe,Mn)2O3],

• calamine [Zn2(OH)2SiO3], and

• smithstone (ZnCO3)

Zinc ores normally contain 5–15%

zinc

18
19
Energy and mass balance on a Unit Operation

20
• The basic equation in materials balances is the law of conservation
of matter

• For each element x we have:

in j m

 m (% x)   m (% x)  m
i 1
i
j 1
j x

Input = Output + accumulation

• When a furnace lining is eroded mx  0
• At steady state conditions mx  0

21
Types of Reactor in extractive metallurgy

Solid in Fluid out gas out + dust Blast gas

Fixed bed reactor Shaft furnace Fluidized bed Retort

22
Types of Reactor in extractive metallurgy

Pneumatic/top
Reverbatory furnace Electric arc furnace blown converter

23
24
25
26
27
28
• The efficiency of an extraction process may conveniently be expressed
by two figures:
o the recovery
o the ratio of concentration

• the recovery is the amount of a given element in a given product

relative to the same element in a raw materials

• the ratio of concentration is of particular importance in ore-dressing,

and is equivalent to the weight of the raw material (the ore) relative
to the weight of the valuable products (the concentrate).

29
30
31
Photomicrograph of Mineral Grains & Assemblage

32
Photomicrograph of Mineral Grains & Assemblage

33
Reactor Design

34
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38
39
40
41
42
43
44
45
46
47
Cross-section of a Pierce-Smith converter, during (a) a slag-blow and (b) a copper-blow

https://doi.org/10.3390/pr8111478
48
49
 Retention time in reactors
• How long the material has stayed in the reactor is retention time

• For batch process such as fixed bed or steel converter, all materials
has stayed within the reactor for the time of the process

• For continuous reactors such as shaft furnace or fluidized-bed

furnace, it is difficult to predict the retention time

• In this situation, two extremes can be distinguished: the perfect

displacement and perfect mixing

• Perfect displacement also known as plug flow is approximately

realized in a shaft furnace

50
• In the ideal shaft furnace, all the material moves parallel and with
the same velocity and the retention time is the same for each piece
of material

• If the feeding rate is m(kg/h )

• The mass inside the reactor is M (kg )

M
• Then, the retention time of the material is (h )
m
• In reality, the displacement of the materials inside the reactor is not
perfect, i.e., the materials along the walls will due to friction tend to
descend more slowly than the materials at the middle.

Average retention time, t m 51

• Assume that at a time t = 0, a small ore particle with quantity of no is
introduced into the reactor

• After a certain time t, the quantity remaining in the reactor is n and

its concentration is n/M
dn
• The rate at which it overflows is   (n / M )m
dt
Total arte of
• Integrating, we will obtain the following overflow

dn m 1
   dt   dt
dt M tm
• Inserting the limits n = no at t = 0, and n = n at t = t, we get
n
 e t / tm  e   r
n0 52
• r is the fraction of the material which remains in the reactor at a
time t and this has a retention time equal to or larger than t

• t/tm is the relative retention time

• Furthermore, the fraction of material which has a retention time

between t and t + dt will be
1 
 dr  e dt  Edt
tm
age distribution function

• For perfect mixing, e 

E
tm

• For t =0, -dr/dt will have its largest value of 1/tm and will decrease
with increasing time 53
54
• All particles in a reactor must have some retention time and it is
evident that


 E dt  1
the area under the curve in
the previous figure
0

• For the case of an ideal plug flow reactor, E would be infinitive at t = tm

and zero at any other t values

Granulated Materials

• metallurgical feed comes as a broken or

granulated material of non-uniform size
and shape

• To describe such materials, we need to know their average size and

shape as well as their size distribution 55
• the average size and shape may be described by two quantities:
o the particle diameter and
o the mean diameter
• The particle diameter, dp is equal to the dimeter of the sphere which
has the same volume, V, as the particle
1/ 3
 6V 
dp   
  
• The mean diameter, dm is quantity that can be defined by the
equation
6V
dm 
A Surface area of the particle

• The ratio between the two expression is termed as a shape factor

d m  1/ 3 (6V ) 2 / 3
p  
dp A 56
 p is unity for spherical and less than unity for non-spherical

• size distribution of the feed can be determined by screening

• Screening is mechanical separation of particles according to their

size.

• The screen analysis could be given on a cumulative basis by giving

the percentage of material which either passes or is stopped by
each screen size
• The void fraction, ε, in a bed of broken solids
expresses the fraction of the bed which is not
occupied by the solids, and may be calculated
from
volume of solids m / s
1   
volume of bed volume of bed 57
• For close packing of spheres of uniform size   0.26

• For loosely packed beds of most broken solids,   0.4 - 0.7

• Smaller void fractions can be obtained by mixing two fractions of
greatly different diameters, where the small particles will fill the
voids between the larger particles

58
 Heat transfer in Reactors
• Heat transfer is the result of the second law of thermodynamics,
which states that the heat will flow from high to low temperature
until equal temperatures are obtained

• The rate of heat transfer is partly determined by the temperature

difference, ΔT, between the heat source and the heat sink and partly
by the resistance to the heat flow

• the resistance to the heat flow can be dependent on the mechanism

of heat transfer:

o Conduction

o Convection

o Radiation 59
 Heat Conduction

• For the flow of heat through a body, the Fourier equation applies

Thermal conductivity
of the material Temperature gradient


 dT 
q  kA 
The quantity  ds 
or flux of heat
per unit time Distance through
Area through which
the heat flows which heat flows
• The minus sign indicates the heat flows towards the lower
temperature 60
• By integration, we have
s2 T2
 ds
q     kdT
s1
A T1
• If A and k are independent of s and T, respectively, we have
 T
q  kA
s
• If k is a function of T, for example as k = a +bT, then the mean value,
kmean = a + b (T1 + T2)/2 may be used

• For a different geometric shape, A can be a function of s

• For a radial heat flow in a cylindrical body, A = 2πrL, where r is the

distance from the cylinder axis and L is the length of the cylinder61
• This gives:
s2 r2
ds dr ln(r2 / r1 ) 2.3 log(r2 / r1 )
s A  r 2rL  2L  2L
1 1

• If k is a independent of T, or by applying a mean value for k the heat

flow becomes
 2LT
q  k
2.3 log(r2 / r1 )

• As 2πL Δr = (A2-A1) and r2/r1 = A2/A1, where A1 and A2 are the areas at
r1 and r2, respectively, then,
 ( A2  A1 ) T
q  k
2.3 log( A2 / A1 ) r
62
 Heat Convection

• This is transfer of heat between

solid surfaces and the fluid (gas or
solid) or between two fluid phases

• The interface between the two phases gives a certain resistance to

heat transfer

• The heat flux will be a function of the interface area A, the

temperature difference, ΔT, and the heat transfer coefficient by
convection hc

q  hc (T ) A
63
• Heat convection can be free and forced convection

• The free convection is where the motion of the fluid near the
interface is caused by temperature differences in the fluid.

• It is useful for calculation of heat losses from the outer shell of a

metallurgical reactor to the surrounding atmospheres

• The forced convection is where the fluid moves relative to the

interface as a result of an external force and the forced convection
has greater importance than the free convection in metallurgical
reactors

• The forced convection heat transfer coefficient is a function of : -3

6 k
o Size and geometric shape of the interface e
pl boo
o The temperature and physical properties of the fluid xam ext
o Velocity of the fluid relative to the interface e E ft
olv 3 o
o Fluid flow type (laminar or turbulent) S .15 64
p
 Heat Radiation
• For radiation from a blackbody surface into open space, Stefan-
Boltzmann law applies
 
q  KT A 4
q  5.67(T / 100) 4 A [W]

• For nonblackbodies, the above expression is to be multiplied by

emissivity of the surface, ε
• For radiation from one surface to another of lower temperature,

 

q  5.67 F (T1 / 100) 4  (T2 / 100) 4 A1 [W]

Efficiency factor

65
 Reaction Kinetics

Homogeneous reaction Heterogeneous reaction

Reaction that takes place in Reaction that takes place

one single phase in more than one phases

• Almost all metallurgical reactions are based on heterogeneous

reaction
• For example:
o between gases and solids as in roasting and reduction
o Two liquid phases as in slag reactions
66
Homogeneous reaction
• Consider the following reactions

lA  mB  nC
• In a phase of a given volume V, there are nA moles of A, nB moles of
B and nC moles of C

• The molar concentration of the three species are then,

nA nB nC
C A  , C B  , CC 
V V V
• The rate of reaction may e expressed as:
dnC dCC n dC A n dC B
rc    
Vdt dt l dt m dt
t is the reaction time 67
• The rate is a function of :
o Concentration of A, B, and C and
o temperature

• If the reaction is the result of the simultaneous collisions of l

molecules of A with m molecules of B to form n molecules of C,
and n molecules of C may collide to form of l molecules of A and m
molecules of B (reverse reaction), then, the rate may depend on
composition
dCC
rc   k1C AC B  k 2Cc
l m n

dt

Rate of constants, and are

functions of temperature
• At equilibrium, the forward and reverse reactions are equal and
the net rate is zero 68
• At equilibrium:

(Cc* ) n k1
* l * m
  Kc
(C A ) (C B ) k2

• k1 and k2 are independent of concentrations, it follows that

k1  K c k 2
• The exponents l, m, and n are the order of reactions with respect
to A, B, and C

• The total order in the forward direction is = l+m, and the

reverse reaction is given by n
69
• The effect of temperature on reaction rate

o The rate constants k1 and k2 increase with increasing

temperature.

• Arrhenius developed the following equation:

E Activation energy

k  k0e RT
Absolute temperature
the universal gas constant
the frequency factor

E
• Linearization of the above equation yields: log k  log k 0 
RT
1
• The plot of log k vs yields linear plot and the slope
T gives the activation energy
70
• If A B, according to Eyring theory, A* represents an activated
compound formed intermediately.

• The activated compound is in chemical equilibrium with A.

• Therefore, a *A  K *a A

Chemical activities of A* and A, respectvely

• K* is the equilibrium constant for the reaction A  A*

• The decomposition of A* into B takes at a universal rate, which is

independent of the nature of the reaction

• It is only dependent on the concentration of A*

71
 *
dC RT *
 A
CA
dt Nh

Avogadro’s number Planck’s Constant

• The concentration of the intermediate compound can be expressed

in terms of its standard Gibbs free energy
  G *
C A*  C A exp( )
RT
• Then,
dC *
RT * RT  G *
A
CA  CA exp( )
dt Nh Nh RT
• from 
dC A dC A
 kC A  k   and G *  H *  TS *
dt C A dt 72
• We have the following

RT  G RT*
S  H * *
k exp( ) exp( ) exp( )
Nh RT Nh R RT

 H *
 k0T exp( )
RT

R S *
exp( )
Nh R Temperature independent

73
 After some time
Diffusion

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles

dn A dC A
JA    DA
dt ds
74
 • For a volume element of unit cross section with a thickness Δs

• The entering flux will be

 dC A 
J A   DA  
 ds  s
• The effluent flux will be
 dC A 
J A   DA  
 ds  s  s 75
• The differences in the flux will be the increase in the amount of A
species within the volume element

dn A dC A  dC A   dC A 
 s   DA    DA 
dt dt  ds  s  ds  s  s
• When Δs goes to zero, we have

dC A d  dC A 
  DA  Fick’s second law
dt ds  ds 
• When DA is independent of s, we have
2
dC A d CA
 DA 2
dt ds 76
 Phase Separation
• Extractive metallurgy would be impossible without phase separation
and this can be illustrated by the carbothemric reduction of iron
oxide to form iron and carbon monoxide gas
Fe 2 O 3 ( s )  3C(s)  2Fe(s)  3CO(g)
• Ore sizes from mine is in between 0.1 -1 m and the first part in any
ore-dressing process involves crushing and grinding which is
commonly referred to as comminution
Comminution

Crushing Grinding

• Crushing and grinding are usually carried out in a sequence of

operations by which the lump size is reduced step by step

• The first or primary crushing, down to 100 mm can be done by: 77

Jaw crusher

78
gyratory crusher

79
gyratory crusher

80
impact crusher

81
• The secondary and tertiary crushing from 100 mm to 10 mm lump
size may take place in:

cone crusher

https://www.youtube.com/watch?v=ImrcDMqW6p0
82
roll crusher

https://www.youtube.com/watch?v=or2vD3vxeAo&t=26s 83
Hammer mills

84
• The final reduction in size usually takes place in
rod mills: uses steel rods as the grinding media in tumbling mills

ball mills

Reading Assignments:

- Energy requirements
in Crushing 85
Screening: mechanical separation of particles according to size

86
Screening

87
Screening

Particle size = 1651 μm

Particle size = 74 μm
Particle size = 37 μm

88
Classification of particles
• Classification of particles is according to settling velocity in
o air
o water
o other fluids
• The terminal settling velocity of a particle in the laminar range can be
derived from Stokes’ Law.
density of the density of the fluid
mean diameter particle
of the particle acceleration of
gravity
d (s   )g
2
v m
18
terminal settling viscosity of the
velocity in laminar fluid
range 89
• In the turbulent region from the Newton’s or Rittinger’s law, we have
1/ 2
 3d m (  s   ) g 
v 
  
• The settling velocity depends not only on the diameter of the
particle, but also on the density of the particles as well as on the
density and viscosity of the fluid

• Assume that the material contains two materials of diameters d1 and

d2 as well as densities of ρ1 and ρ2 . Then Stokes’ law can rewritten
for a laminar range as
1/ 2
d1   2   
 
Free settling ratio
d 2  1    under laminar
conditions 90
Free settling ratio under turbulent conditions will be

d1  2  

d 2 1  

Concentrations
• The most important concentration processes are:

1. Sorting

2. Gravity separation

3. Flotation

4. Magnetic and electrostatic separation 91

Sorting:
• is the oldest ore-dressing method.

• Some sorting was done at the mine site where barren rock and sub
marginal rocks were discarded

• After primary or secondary crushing, manual sorting can be carried

out

• Mechanical sorting uses

sensors of magnetic, electric,
or radioactive properties
based ore sorting

92
Sensor-Based Ore Sorting Technology in Mining—Past, Present and Future
https://doi.org/10.3390/min9090523 93
Gravity separation: is based on the difference in densities of the
components

94
Flotation: is based on the ability or lack of ability of different surfaces to
be wetted by water • The wettability of a surface is
determined by the relative values
of interfacial energies:
o solid-water
o Solid-air
o Water-air

• If the solid-water interface

energy is larger than the two,
then water will not cling on the
surface of the solid and then the
solid is hydrophobic

• If the solid-air interface energy is

larger than the other two, then
the surface is hydrophilic surface
95
Magnetic separation: based on the difference in magnetic properties of
the minerals
• A few minerals such as metallic
iron, magnetite (Fe₃O₄), and
some form of pyrrhotite (Fe(1-x)S
(x = 0 to 0.2)) are ferromagnetic
and are attracted by a magnet

• A number of other minerals such

as ilmenite (FeTiO₃), hematite
(Fe₂O₃), and other iron minerals,
and garnet (a group of silicate
minerals) are weakly attracted
and are paramagnetic

96
Magnetic separation: based on the difference in magnetic properties of
the minerals

97
Electrostatic separation: is based on differences in electrical
conductivity of the minerals

98
Electrostatic separation: is based on differences in electrical
conductivity of the minerals

99
Electrostatic separation: is based on differences in electrical
conductivity of the minerals

Illustration of electrostatic separation process in the example of a drum type separator (a)
and free-fall type (b). Taken from : https://doi.org/10.3390/s20247201 100
 Solids from liquids separation
• In many hydrometallurgical processes, the valuable metals from the
concentrate may be obtained as a precipitate from an aqueous
solution
• In order to obtain the valuable element in a concentrated form, it is
necessary to remove the water
• This can be done by thickening and filtration
• Thickening principle can be studied
using an aqueous suspension of solids
in a measuring cylinder
• After some time, we observe four
different layers
o Practically clear water (A)
o diluted suspension (B)
o more concentrated suspension (C)
o Almost solid cake (D) 101
• Thickening mechanism can be distinguished between the following
1. Free settling zone B
2. Hindered settling zone C
3. Exudation of water in zone D
• As the particle size decreases, the settling velocity decreases and
would approach to zero for the smallest particles

• For these small particles, the velocity can be increased by

flocculation, i.e., the individual particles are made to adhere to
each other to form flocs of larger diameter

• Flocculation can be promoted by addition of chemicals such as:

o lime
o alum with the general formula XAl(SO4)2·12H2O, where X is a
monovalent cation such as potassium or ammonium
o starch, and
o certain soluble polymers 102
103
Fuel and Ore Preparation
• Coal, coke, oil, and gas represent an important raw materials for
metallurgical industry and are used as a fuel and reducing agent

• Chemical compositions of coal, mineral oil, and natural gas is made

up of carbon and hydrogen with a minor amounts of other elements
such as nitrogen, sulfur, and oxygen

• The atomic ratio nH

 1 for coal
nC

nH
2  3 for mineral oils
nC

nH
 4 for methane (CH 4 )
nC 104
• Coal and to a lesser extent oil, contain varying amount of ash,
consisting of metal oxides and silicates.

• When the coal or the oil is burned, the ash remains behind
unreacted and are usually regarded as a burden on fuel and lower its
economic value

• Most coal contains sulfur which may occur partly as inorganic

sulfides, e.g. pyrite (FeS2) and partly chemically bonded to the
hydrocarbons

• When the coal is burned, sulfur enters the combustion gases as SO2
and the sulfur may contaminate the metal when coal is used as a
reducing agent and thus regarded as harmful

105
Stable at room
temperature

106
• Gibbs energy of formation in coal is related to one mole of carbon as
standard states, which is usually graphite and is stable at
atmospheric conditions

• At room temperature, methane (CH4) and ethane (C2H6)are stable

• At temperatures above 500 °C, CH4 decompose into graphite and

hydrogen

• If the original materials contains oxygen, then this will react with
graphite and hydrogen to form CO2 and H2O, respectively, and forms
CO at higher temperature

• Nitrogen is present in some coals and organic compounds, and on

heating, it will partly decomposed to ammonia, but since ammonia is
not stable itself, the final product will be nitrogen gas.
107
• The composition of coal, coke, and oil may be expressed by their
proximate and their ultimate analysis

• proximate analysis gives the percentage of moisture, volatile matter,

fixed carbon, and ash

• ultimate analysis gives the percentage of individual elements such as

carbon, hydrogen, nitrogen, sulfur, and oxygen as well as the ash-
content and all are expressed on moisture free basis

• The heat of combustion of the fuel may be estimated from the

ultimate analysis using Dulong formula
Moisture percentage

NCP  338C  1423( H  O / 8)  92S  24.4(9 H  M )

Net Calorific Power, in Kilojoules per kilogram 108

Coking of Coal: is the process of heating coal in the absence
of air Coking of Coal

Low-temperature Coking high-temperature Coking

- up to 500 °C - up to 1000 °C
- Char will be obtained that - The gas is rich in hydrogen and
contains considerable methane
amounts of hydrogen - Higher hydrocarbons and tars
- The evolved gas is rich in have been cracked (decomposed)
hydrocarbons and tar under the influence of high
- Can be used in smokeless temperature
household fuel and - The gas contains CO, CO2, H2O,
reducing agent in C2H6, H2S, and NH3
ferrosilicon production - The product is low in volatile
- Limited metallurgical components (1-2%)
application - Exclusively used in metallurgical
applications 109
Gasification of coke and coal
• The entire carbon content of the coal can be converted gaseous
products, which may be done by partial combustion with air, oxygen,
steam, or carbon dioxide.

• This can be done in gas producer by gasification process using, for

example, low shaft furnaces in which air+steam is fed through
bottom grate of the furnace

• Between the carbon and oxygen, the following exothermic reaction

occurs
C  O2  CO2 , G1o  394100  0.8T J (1)
2C  O2  2CO, G o2  223400  175.3T J (2)
• By subtraction, the “Boudouard” reaction is obtained, which is highly
endothermic:
CO2  C  2CO, G 3o  170700  174.5T J (3) 110
Gasification of coke and coal

111
• If steam is used with air, it reacts with carbon above the grate
according to the following endothermic reactions

H 2O( g )  C  H 2  CO, G o4  134700  142.5T J (4)

Partial decomposition of Oil and natural gas

• On heating, hydrocarbons decompose and deposit soot particles and
therefore they have to first converted into simple gases, CO, and H2

• This is achieved by partial combustion with air or oxygen

• For partial decomposition of methane, the following reaction is used,

which is slightly exothermic

2CH 4  O2  2CO  4 H 2 , H 298  71 kJ

112
• To obtain a temperature above 1000 °C, which is necessary to obtain
a good conversion and prevention sooting, the air must be preheated
or pure oxygen may be used

• For gasification of oil, the danger of sooting is even higher and special
burners are developed for this purposes

• Reforming of natural gas or oil by means of steam would be of the

type:
CH 4  H 2O  CO  3H 2 , H 298  206.3 kJ

• This is endothermic reaction and extra heat has to be supplied, by for

example, electricity or regenerative heating

• If a natural gas is reacted with oxygen at 2000 ° C, acetylene may e

formed
3
2CH 4  O2  C2 H 2  3H 2O 113
4
 Drying and calcination
• Calcination involves the removal of water carbon dioxide, or other
gases, which are chemically bound as hydrates or caronates

• Hydrated metals such as • Decomposition temperature

Al2O3 , water removal is of well defined carbonates by
carried out at 1000 °C calcination 114
Heat balance for shaft furnace calcination

115
116
117
118
Roasting of sulfides
• Roasting is the oxidation of metal sulfides to give metal oxides and
sulfur dioxide

• Typical examples include:

2 ZnS  3O2  2 ZnO  2 SO2

2 FeS  5.5O2  Fe2O3  4 SO2

• Typical ores which are roasted are sulfides of copper, zinc, and
lead

• In this cases, the main purpose is to convert the metals, partly or

completely into oxides for subsequent treatment

• The sulfur dioxide is then byproduct 119

• Roasting is usually carried out below the melting points of the
sulfides and the oxides involved, usually below 900 – 1000 °C
Thermodynamics of roasting
• The necessary conditions for the formation of the various roasting
products may be illustrated by the equilibrium relations in a
system which contains metals, sulfur, and oxygen

• Here we have 3 components and according to phase rule, we can

have a maximum of five phases, i.e., four condensed phases and
one gas phase

• The gas phase contains normally SO2 and O2; but also SO3 and even
S2 may be present
• Among these gaseous compounds, the following equilibria exists
S 2  O2  2 SO2
2SO2  O2  2SO3 120
121
122
Reading assignment

- Kinetics of roasting
- Technology of roasting
- Agglomeration
- Pelletizing

123
Volatile Metals

124
125
126
127
Reading Assignments:
- Production of volatile metals
- Theory of zinc oxide reduction
- Industrial zinc processes
- Refining of zinc by distillation
- Zinc fuming
- Magnesium

128
 Hydrometallurgy and Electrometallurgy

Hydrometallurgy

• Extraction, recovery and purification of metals, through

processes in aqueous solutions

• Metals are also recovered in the other forms such as oxides,

hydroxides.

Electrometallurgy

Recovery and purification of metals through electrolytic

processes by using electrical energy.
 Hydrometallurgy
• Traditionally, hydrometallurgy is emphasized for metals extraction
from ores

• Hydrometallurgical processing may be used for the following

purposes:
- Production of pure solutions from which high purity metals can be
produced by electrolysis, e.g., copper, zinc, nickel, gold, and silver

- Production of pure compounds which can be subsequently used for

producing the pure metals by other methods. For example, pure alumina to
produce smelter grade aluminum

• However, hydrometallurgy principles can be applied to a variety of

areas such as metals recycling from scrap, slag, sludge, anode
slime, waste processing, etc.
 Unit Processes in Hydrometallurgy

• In general, hydrometallurgy involves 2

(two) main steps:
1. Leaching
Selective dissolution of valuable
metals from ore
2. Recovery
Selective precipitation of the desired
metals from a pregnant-leach
solution.
General outline of hydrometallurgical
processes
Ore/concentrate
Oxidant Leaching agent

leaching

Solid-liquid separation Solid residue to waste

Pregnant Solution

Precipitant or
electric current
Solution purification

Precipitation

Pure compound Metals

• Commonly, solution purification is conducted prior to metals
recovery from the solution.
• Solution purification is aimed at obtaining a concentrated
solution from which valuable metals can be precipitated in
the next processes effectively
• Solution purification methods which are commonly used are
as follows:
• Adsorption by activated carbon
• Adsorption by ion exchange resins
• Solvent extraction (using organic solvents)
• Precipitation with metals (cementation)
Solution purification

• Solution purifications by adsorption with activated

carbon, ion exchange resins (IX) and solvent
extraction (SX) have the same unit operations,
namely:
• Loading, and
• Elution
• In the elution step, the adsorbers are usually
regenerated for another process cycle.
 Hydrometallurgy development
 Hydrometallurgy is developed after pyrometallurgy.
Metals smelting has been practiced since thousands
years ago.
 Hydrometallurgy was developed after the people
discovered acid and base solutions. However, modern
hydrometallurgy development is commonly associated
with the invention of Bayer Process for bauxite leaching
and cyanidation for gold extraction at the end of 19th
century (1887).
 One of important highlights of hydrometallurgy
development is uranium extraction (Manhattan Project)
aimed at nuclear weapon production in second world
war (1940‘s).
 Important milestones in the development of
hydro-electrometallurgy
• Cementation & Aqua Regia Use - 8th Century
• Cyanidation - 1887
• Bayer Process - 1887
• Hall-Heroult Process - 1886, 1888
• Copper Electrowinning - 1912
• Zinc Electrolytic Process - 1916
• Manhattan Project (IX/SX) - 1940’s
• Biooxidation of Sulphide Concentrates - 1960’s
• Pressure Leaching
– Sherrit Gordon Nickel Process - 1954
– Pressure Acid Leaching of Ni Laterites - 1955
• Large Scale Copper SX/EW - 1960’s
Important milestones in the development of
hydro-electrometallurgy
• Carbon in Pulp (CIP)/Carbon in Leach (CIL)
for Gold Recovery - 1980’s
• Pressure Oxidation of Zinc Sulphides - 1981
• Two-Stage Zinc Pressure Leach - 1993
• Atmospheric Leaching of Zinc Sulphides
– Albion (1993), Outokumpu (1999)
Recent Developments:
• Skorpion Project (Anglo American) – 2003 (Zn from ZnS)
• Hydrozinc (TeckCominco) - 2004
• Inco’s Goro and Voisey Bay Projects - 2007
• Leaching of Chalcopyrite (CuFeS2) Ores
-Hydrocopper (Outokumpu)  Cu from sulfidic ores
•Atmospheric leaching of nickel laterite ore: 2008?
Hydrometallurgy vs. Pyrometallurgy

Hydrometalurgy Pyrometallurgy
Treat high grade Less economic More economic
ore?
Treat low grade ore? Possible with Unsuitable
selective leaching
Treat sulphide ore No SO2; otherwise So SO2 generated (can
or SO42- are be converted to
generated H2SO4)
Separate similar Possible with certain Not possible
metal, such as Ni method
and Co
Pollutant Waste water, Gases and dust
solid/slurry residues
Reaction rates Slower Rapid
Hydrometallurgy vs. Pyrometallurgy

Hydrometalurgy Pyrometallurgy
Scale of operation? Possibly economic to Unconomic at smale
be done at small scale operation
scale operation and
expansion is easier
Capital cost Generally lower than Higher
pyrometallurgy
Energy cost Lower Higher
Materials Handling Slurry Easy to be Handle Molten
Pumped and Metal, Slag,
Transported Matte
Residues Residues – Fine Slags – Coarse
and Less Stable and Stable
Spontaneous Reaction, Equilibrium State
• As has been learned in basic engineering courses,
chemical reaction will spontaneously occur when the
Gibbs free (G) < 0.
G = Go + RT ln K
• G = 0  process is in equilibrium state
• Go = standard Gibbs free energy
• R = ideal gas constant = 8,314 J/K.mol
• T = absolute temperature of the system (K)
• K = equilibrium constant
• Standard Gibbs free energy is determined at:
• Gaseous components partial pressure = 1 atm
• Temperature = 25 oC (298 K)
• Ions activity = 1
Equilibrium Constant

• For reaction:
aA + bB  cC + dD

K
 C   D
a c a d
a
A = activity of A = γ[ A ] → [ A ] = A concentration
 A  B 
a a a b

 = activity coefficient of
component A

For gaseous component of X→ a X = γ p X,

in which p X = parsial pressure of X
Nernst Equation
• Hydro-electrometallurgical processes often involve
electrochemical reactions.
• For electrochemical reaction
G = -nFE, Go = -nFEo, therefore

RT
E E o

nF
ln K Nernst Equation
In which,
E = potential for reduction-oxidation reaction
Eo =standard potential for reduction-oxidation reaction
n = number of electron involved in the electrochemical reaction,
F = Faraday constant = 96485 Coulomb/mole of electron

• Spontaneous process  E > 0  G < 0

Chemical reactions usually
perform in leaching processes
• Dissolution by acid
• Example: ZnO(s) + 2H+ → Zn2+(aq) + H2O(l)
• Dissolution by base
• Example: Al2O3(s) + 2OH- → 2AlO2-(aq) + H2O(l)
• Dissolution by complex ion formation
- Example: CuO(s) + 2NH4+(aq) + 2NH3(aq) →
Cu(NH3)42+(aq) + H2O(l)
 Chemical reactions usually
perform in leaching processes

• Dissolution by oxidation

• Ex: CuS(s)+ 2Fe3+ → Cu2+(aq) + 2Fe2+ + So(s)

Other oxidators: O2, ClO-, ClO3-, MnO4-, HNO3,

H2O2, Cl2

• Dissolution by reduction mechanism

• Ex: MnO2(s) + SO2(aq) → Mn2+(aq) + SO42-(aq)

Correlation of free energy (G)
and heat (enthalphy = H)

G = H - TS
Go = Ho - TSo
∆Ho = Standard enthalpy (kJ/mol)
∆Go = Standard entropy (kJ/mol)

∆Go (reaction) = ∆Go (products) - ∆Go (reactants)

∆Ho (reaction) = ∆Ho (products) - ∆Ho (reactants)
∆So (reaction) = ∆So (products) - ∆So (reactants)
T
ΔHT = ΔH298 + ∫ Cp dT
298
Cp = heat capacity at constant pressure (J/molK)
Where possible, processes are designed to be autothermal →
maintain constant temperature by the heat given by the reaction
Pourbaix Diagram

• Pourbaix Diagram = Potensial (Eh) – pH

Diagram.
• The diagram represents thermodynamic
equilibrium of metal, ions, hydroxides (or,
oxides) in aqueous solution at certain
temperature (isothermal).
• The boundary of stability regions of metal,
ion, hydroxides (or oxides) are equilibrium
lines.
• Does not reflect reaction kinetics.
Pourbaix Diagram

• Three possible types of equilibrium lines:

• Horizontal
• Vertical
• Slope
• Variations in ion activities are plotted as
contours/dashed lines
• Horizontal Line: for equilibrium reactions that
are independent of pH.
Horizontal Line
• Example:

Fe3+ + e = Fe2+ Eo = 0.77 V

R = 8.314 J/Kmol, T = 298 K, F = 96500 C/mol e-, n = 1 mol e-
o RT aFe 2 +
E =E - ln
nF a Fe3 +
If all ion concentrations are assumed to be equal to
their molar concentrations  10-6 M.

o RT [ Fe 3+
] E = 0,77 -
8,314 x 298 [ Fe 2+ ]
ln
E =E - ln [ Fe3+ ]
nF [ Fe 2+ ] 2x96500
[ Fe2+ ]
E = 0,77 - 0,0592 log
[ Fe3+ ]
E = 0,77
Vertical Line
• Reactions do not involve electron → n = 0, no
potensial , the equilibrium depends only on pH.
• Example:

Fe2O3 + 6H+ = 2Fe3+ + 3H2O

K = [Fe3+]2/[H-]6
pH = - loga H+ ≈ - log[ H+ ] = 14 - pOH
- log[ OH]
-
pOH = - loga (OH)- ≈

For certain Fe3+ concentration we can determine the

equilibrium pH for the above reaction.
Slope Line
• For reactions that depend both on potensial
(Eh) dan pH.
• Example:

If all ion concentrations are assumed to be equal to

their molar concentrations  10-6 M.
Water stability region (dotted lines)

• Upper boundary line

 At pO2 = 1 atm

• Lower boundary line

 At pH2 = 1 atm
Eh-pH diagram of Fe-H2O system at 25°C
Eh-pH Diagram of Zn-H2O System at 25 oC.
Eh-pH Diagram of Cu-H2O System at 25 oC.
Application of Eh – pH diagram in
hydrometallurgy

• Predicting potential leaching behaviour for

certain mineral system
• Predicting the possibility of metals ion
precipitation at the purification of pregnant-
leach solution
Application of Eh – pH diagram in hydrometallurgy

Fe(OH)3 or Fe2O3 can be precipitated from Fe3+ at lower

pH than the precipitation of Zn2+ to Zn(OH)2 or ZnO.
Fe2+ have to be oxidized to Fe3+ to gain lower pH value for
Fe(OH)3 precipitation.
Pourbaix Diagram can be constructed at various
temperature for more than two systems

Eh-pH diagram of Zn-S-H2O system at 25oC

Diagram Pourbaix in Presence of Complex Ion

• Example: Au-H2O system with the presence of cyanide (CN-) ion

(case of gold cyanidation leaching)
• Equilibrium of Au3+/Au

Au3  3e  Au (1)
G 0  G 0 f (Au)  G 0 f (Au3 )
 433 KJ / mol
Standard reduction potential for Reaction 1:
0 3
 G 433  10
E0  
nF 3  96500
 1.5 V
• Equilibrium reaction of O2/H2O

O 2 + 4H + + 4e = 2H 2 O (2)
Eo = 1.23 V.

Au3+ / Au = 1.5
E > EO2 / H2O
O 2 / H2O = 1.23 Au3 + / Au

Therefore, Au3+ ions are not stable in water and readily reduced to Au
by oxidation of H2O to O2 (the opposite of Reaction 2). In the other
word, gold can not be oxidized (dissolved) in water only with the
presence O2.
Potensial – pH diagram of Au–H2O system without
the presence of complexing agent
With the presence of CN-, Au3+ forms STABLE
COMPLEX of “aurocyanide“ (Au(CN)2-) and the potential-
pH diagram for Au changes significantly as follow:

Eh-pH Diagram of Au-CN-

H2O system at 25 oC for [Au]

= 10-4 M and [CN-] = 10-3 M
• By the presence of cyanide ions,
Au+ + e = Au E = 1.69 – 0.0591 log [Au+]
Au+ + 2CN- = Au(CN)2- (K = 2 x 1038)
Au(CN)2- + e = Au + 2CN- ........................... (3)

E  1.69  0.0591 log K  0.0591 log  CN  / a Au CN  2
a  2 

In comparison to the first reaction that has Eo of 1.69 V,
Reaction (3) has much lower Eo at -0.57 V.

Dissolution of Au is limited by the following equilibrium of

Reaction (3).
• During cyanidation leaching, dissolved oxygen is required to
oxidize Au prior to the formation of stable complex of Au(CN)2-.
 Interactions in Electrolyte Solution
Two types of interactions in electrolyte:
- Ion-ion interaction, and
- ion-solvent interaction

Knowledge of interaction in electrolyte solution is important because the

interactions affect solvation effects, diffusion, conductivity, ionic strength
and activity coefficients of ions in solution.

Interactions in electrolyte solution influence the transport properties of

ions in solution.
 Ionic Strength and Activity Coefficient
- Ionic strength (I), expresses the ionic concentration
that includes the effects of ionic charge.
- Ionic strength (I) is defined as follow:
1
I   ci z i
2

2 i
in which ci = concentration of ion i in molar (mol/L)
and zi = the charge of ion i.
- It is found that activity coefficient, electrical
conductivity and the rates of ionic reactions are all
the functions of ionic strength.
Ionic Strength for unit concentration in molal
- Remember, molality = moles of solute in 1 kg
solvent. Molality can be converted to molality by the
following correlation:
ci
mi =
0.001ρ - ∑ c iMi

in which Mi = the molar mass of each solute in

kg/mol (not in g/mol), ci = molarity of solute i, and 
is the density of the solution in kg/m3 (=g/L)
- In dilute solutions, ci  0.001mio (in which o =
density of pure solvent).
Ionic Strength for unit concentration in molal
- Therefore for dilute solution,

1 1
I= ∑ c i z i = ∑ 0.001m i ρ o z i 2
2
2 i 2

0.001ρo 2
I= ∑ mi z i
If the solvent is water2at 25oC (density  1000 kg/m3), then:

1 Similar form with ionic

I ≈ ∑ mi z i 2 strength in molarity
2i
- Molar activity coefficient can be converted to molal
activity coefficient by the following correlation:)

f
 
1  M s  m

for salt, or

fi
i  for single ion.
1  M s  m

in which  = total moles of ion formed during

complete dissociation, m = ionic molality and Ms =
molecular weight of solvent (kg/mol).
Activity and Activity Coefficient,
DEBYE-HUCKEL LAW

- Debye Huckel Law correlates the activity coefficient (fi , i)

with ionic strength (I).
- Forms of Debye-Huckel equations depend on
concentration of solution and the unit concentration used.
- For dilute solution at 25 oC and I given in molar (M),

2
log f i  0.51159 z i I for single ion, and

log f ± = 0.51159 z + z - I for salt.

- The above equations are known as LIMITING DEBYE
HUCKEL LAW.
The limitation of LIMITING Debye-Huckel Equation

• The D-H Limiting Law is called a ”limiting” law

because it becomes increasingly accurate as the limit
of infinite dilution is approached.

• Up to concentrations of about 0.01m THE LIMITING

D-H LAW gives reasonable values, but at higher
concentrations the calculated activity coefficient
become inaccurate (high %error compared to the
values determined experimentally).
 Debye-Huckel Law for Concentrated Solution

- For concentrated solution (> 0.01 molal), Limiting

Law D-H is modified by considering the ionic size
parameter:

 A z z I
log f  
1  Ba I

- in which A and B are constants that depend on the

kind of solvent and temperature, a = ion size
parameter.
- For aqueous solution at 25 oC, A = 0.51159 and B =
3.2914 x 109 meter.
ACTIVITY AND MEAN ACTIVITY

- Molar activity and molar activity of a single ion i is

determined as follow:
a i   i mi and a i  f i Ci

- For 1 mole of M+A- salt that dissociates to + mol of

Mz+ and - mole of Az-

M+A-  + Mz+ + - Az-

 = + + -
ACTIVITY AND MEAN ACTIVITY

Mean molal activity coefficient can be determined by

the following correlation:


     
 1 /  

Mean molality,

m  m m
 
 1/ 
 
m     

 1/ 
m

Note that m  m

Thus, mean molal activity,

a     m
 Exercise: 1
1. Determine the molar activity coefficient of Ca2+ at 25oC using relevant
Debye Huckel Equation in the following solution:
a. 0.0004 mole of HCl and 0.0002 mole of CaCl2 in one liter solution
b. 0.004 mole of HCl and 0.002 mole of CaCl2 in one liter solution
c. 0.4 mole of HCl and 0.2 mole of CaCl2 in one liter solution
Ion size parameter for Ca2+ = 0.4 nm.
Exercise 2:
2. The stoichiometric mean activity coefficient at 25 oC
of the sulphuric acid in a mixture of 1.5 molal
sodium sulphate (Na2SO4) + 2 molal H2SO4 is
0.1041. If the second dissociation constant, K2, for
sulphuric acid is 0.0102 and the pH of the solution is
–0.671, calculate:
a) the molal activity of H2SO4
b) the molal activity of SO42-
c) the molal activity of HSO4-
d) the mean activity of H2SO4
 Exercise:3
1 gram FeCl2, 1 gram NiCl2 and 1 gram of HCl are added to 200 ml of deaerated
water. Platinum electrodes are used to deliver electrical current so that the
electrolysis performs. The anodic and cathodic current density are 1000 A/m2.
The following are the reactions and Eo (in the reduction direction) that may occur:
Fe2+ + 2e = Fe Eo = -0,277 V
Ni2+ + 2e = Ni Eo = -0,250 V
2H+ + 2e = H2Eo = 0 V
Cl2 + 2e = 2Cl- Eo = 1,359 V

a) Calculate molar activity coefficients of the cations and anion contained

in the solution (use the Finite Size of Debye Huckel Limiting Law)
b) Calculate the activity of the cations and anion contained in the solution
c) Determine the half cell potential of the above reactions
d) Which pair of redox (reduction –oxidation reaction) that would occur (based
on the calculation of c)
 Exercise: 3 (cont.)

e) What would be the cell voltage of the reaction d

Data: Atomic weight Fe = 55.8, Ni = 58.7, Cl = 35.5, H =1

Ion size parameter in nm : Fe2+ = Ni2+ = 0.6, H+ = 0.9, Cl- = 0.3
H2 overpotential = 0.28 V
Cl2 overpotential = 0.03 V
Ohmic overpotential = 0.25 V.
Kinetics in Hydrometallurgy
• Kinetics in hydrometallurgy deals with the kinetics of
leaching, adsorption and precipitation
• Studying of leaching kinetics is done for the
establishment of the rate expression that can be used
in design, optimization and control of metallurgical
operations.
• The parameters that need to be estabished:
• Numerical value of the rate constant
• Order of reaction
• Rate determining step
• Activation energy
 Leaching Kinetics
• Consider the dissolution of a metal oxide, MO, with
an acid by the following reaction:

MO(s) + 2H+(aq)  M2+(aq) + H20(aq)

• The reaction rates for this leaching system can be
given by

dCMO 1 dCH+
rR = - = -
dt 2 dt
or
dCM2+ dCH2O
rP = =
dt dt
Leaching Kinetics

• For general example if a chemical reaction involves A

and B as reactants and C and D as products, the
stoichiometric reaction can be written as follows:

k1
aA + bB ⇔ cC + dD (1)
k2
where
a, b, c, and d = stoichiometric coefficients of species
A, B, C, and D, respectively
k1, k2 = reaction coefficients in the forward and
reverse directions, respectively
Leaching Kinetics

• The rate expression of this stoichiometric reaction can

be written in a more general way:

1 dC A 1 dCB 1 dCC 1 dCD

- = - = = = k 1CnA CBm - k 2CpCCDq (2)
a dt b dt c dt d dt

where
CA, CB, Cc, and CD are concentrations of species A, B,
C, and D, respectively and m, n, p, q are orders of
reaction.
Leaching Kinetics

• However, if the reaction given in Eq. 1 is irreversible, as in most

leaching systems, Eq. 2 is reduced to the following form:

1 dC A
- = k 1CnA CBm
a dt
or
where k1dC
’= k x a.
1A
- = k 1' CnA CBm
dt
• For this system, the rate constant, k1', and the orders of
reaction, n and m, should be determined with the aid of
leaching experimental data.
• The rate expression given in the above equations can be
further reduced if the reaction is carried out in such a way
that the concentration of A is kept constant.
• For such situations, the rate expression is reduced to:

dC A
- = k 1″CBm
dt

where k1”= k1’ x CAn. It should be noted that the rate

constant and the order of reaction are constant as
long as the temperature of the system is maintained
constant.
• Consider the dissolution of zinc in acidic medium:

Zn(s) + 2H+(aq) → Zn2+(aq) + H2(g)

• For the above reaction, the rate of disappearance of H+ ion

is directly related to the rate of appearance of Zn2+ ion;
thus,

dC Zn2 + 1 dCH+
= - = k ′CmZn CHn = kCHn
dt 2 dt
• If concentration of zinc metals is assumed to be constant and C H is further
abbreviated generally as CA, then the equation can be written as follow :

dC A
- = kCnA
dt
• The order of reaction, n, can be any real number (0, 1, 2, 1.3, etc.).
• When n = 0, the reaction is referred to as “zero order” with respect to the
concentration of A.

dC A
- = kC A 0
dt
CA t
o
∫ dC A = C A - C A = k∫ dt = -kt
Co
A
0

where Cor k
A represents the concentration of A at t = 0, and XA represents the
o
XA = o t
fractional conversion,
CA i.e., XA = [ (CAo — CA)/ CAo].
• If the plot of XA versus t gives a straight line, the zero-
order assumption is consistent with experimental
observations and the k value can be obtained from the
slope of the plot.

XA
k/CAo

time

• When n = 1, the reaction is first order with respect to the

concentration of A:
dC A
- = kC A
dt
CA dC A t
∫ = -k ∫ dt = -kt
CA C A
o 0

CA
ln o = -kt
CA
ln( 1 - X A ) = - kt or X A = 1 - e -kt

ln (1 - XA)
k

time
For second order reaction,

CA dC A t
∫ 2 = - k ∫ dt = -kt
o
CA C A
0
XA
(1 - XA) k C Ao k
1 1
- = -kt
C A CoA
XA
= CoA kt
1- XA time

If the second-order assumption is valid, we obtain a

straight line from a plot of XA/(1 - XA) versus t, and the
rate constant can be determined from the slope of the
plot.
Temperature Effect on the Reaction Rate
(Arrhenius Law)
Reaction rate increases markedly with increasing
temperature. It has been found empirically that
temperature affects the rate constant in the manner
shown in the following equation:

k = k o e -Ea / RT

Ea 1
ln k = ln k o -
R T
Ea
o 1
log k = log k -
2.303R T

where Ea is the activation energy and k° is a constant

known as the frequency factor, frequently assumed to
be independent of temperature.
 Modeling of heterogenous reaction kinetics

• Heterogenous reaction between solid and fluid in

hydrometallurgical processes is frequently modelled with
“shrinking core“ model.
• If we select a model we must accept its rate equation, and
vice versa.
• If a model corresponds closely to what really takes place,
then its rate expression will closely predict and describe the
actual kinetics;
• If a model differ widely from reality, then its kinetic
expressions will be useless.
• Detailed of modeling and relevant kinetics equations for
various rate determining steps can be found in previous
course (Metallurgical Kinetics).
• For determination of Ea, number of experiments, at least
at three or four different temperatures are needed, with all
other variables being kept constant. The next step is to
calculate the rate constant for each temperature as
discussed previously.
• A plot of In k versus 1/T yields a straight line from which
the activation energy, Ea, can be determined
• Activation energy value can be used to predict the rate
determining step of the reaction:
• Ea = 40 – 80 kJ/mol: process is controlled by surface chemical
reaction

• Ea = 8 – 20 kJ/mol: process is controlled by diffusion to and from

the surface