HHydometallurgy Handout

HYDROMETALLURGICAL PROCESSES NOTES
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PREPARED BY G. SAKUHUNI, 2008
ChemEng. Minerals Engineering,
NUST
1.0 Fundamentals of Hydrometallurgy
At the end of this section you should be able to:
Distinguish the various hydrometallurgical unit processes
Demonstrate an understanding of the origins of the hydrometallurgical unit
processes
Describe galvanic cells and carry out basic calculations involving galvanic cells
Explain hydrometallurgical reactions on the basis of electrochemical cells
use the Debye-Hunkel limiting rule to evaluate the solubility constant of a
reaction
1.1 Introduction
Hydrometallurgy is a relatively recent technology. Modern, large-scale
hydrometallurgical processing plants depend on electrical power for transport and
agitation of large tonnages of ore slurries and solutions. Pumps, agitators, autoclaves, and
air compressors of the design needed for hydrometallurgical processing are historically
recent developments. Reduction of dissolved metals electrochemically, as in
electrorefining and electrowinning, has broadened the application of hydrometallurgy for
separation and recovery. Prior to the availability of electrical energy, reduction from
solution was possible using chemical reductants, but rarely on a large scale. A noteworthy
example is the reduction of copper contained in acidic mine waters using metallic iron.
Contact reduction of one metal on another, more electronegative metal is commonly
called cementation. This practice was carried out as early as the sixteenth century in
Europe and is common practice today for recovery of copper from acidic leach liquors.
Leaching refers to the process in which solid ores or concentrates are contacted by an
aqueous lixiviant or leach liquor capable of dissolving all or part of the ore or
concentrate. The loaded or pregnant liquor is then subjected to a separation process for
purification or recovery or both of desired metals or metal compounds. The dissolution
processes may involve oxidation and reduction or may be simple dissolution,
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Without exchange and reduction or may be simple dissolution, without exchange of
charge between the solid and the lixiviant. In the former, the lixiviant must contain a
suitable oxidant or reductant for the dissolution process to occur.
1.2 Historical
Hydrometallurgy followed the developments of Michael Faraday who in 1831 provided
the basis that led to the dynamo and to electrical machinery. Electrical energy was
available on a large scale some 40 years later. The first electrolytic reduction plant was
for copper and was constructed near Swansea in 1869.The solvent action of cyanide for
gold and silver was noted as early as 1783 and cyanidation became a commercial process
following patents by MacArthur and Forrest in 1887 and 1889. Nickel and cobalt have
been produced commercially by hydrogen reduction since 1954. The chemistry of
gaseous reduction was understood prior to this time. Patents issued between 1906 and
1941 covered the use of SO2, CO, and H2 as gaseous reductants in pressurized vessels. By
the early 1900s three methods for the direct reduction of metals from aqueous solutions
were available to the metallurgical industry:
(1) Cementation (contact reduction)
(2) Electrolytic reduction, and
(3) Gaseous reduction.
In the period 1946-1956 researchers at Sherritt Gordon Mines, Ltd, in Canada and
Chemical Construction Corporation in the United States developed commercial processes
for leaching of nickel and cobalt sulfides and arsenides. Nonoxidative low-pressure
Leaching of bauxite was developed by Bayer in 1892 and is currently the worldwide
method for the production of high-purity alumina feed for the Hall Herault electrolytic
cell for aluminum metal production. An important step in many hydrometallurgical
processing schemes involves the upgrading of solutions prior to electrowinning or
crystallization. The advent of ion exchange and solvent extraction represented important
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developments for both recovery and upgrading of dilute process streams. Cation
exchange on zeolites was first noted in 1876 by Lemberg and a significant advance
resulted from the work of Adams and Holmes in 1935 when they developed synthetic
ion-exchange resins. Anion exchange became possible and available on a large scale with
increased opportunity for metals extraction. Early attempts in 1945-1950 to recover
uranium by cation exchange were not successful. In 1948, however, H. E. Bross
successfully extracted uranium on anion exchangers. The first ion-exchange plant for
uranium recovery was built in South Africa in 1950. There has been a tendency to place
hydrometallurgy strictly on a competitive basis with smelting for the treatment of base
metal sulfides. Too many overly optimistic and, in some cases, false claims have been
made of the relative virtues of hydrometallurgy compared to smelting. Modem smelting
plants can meet the SO2 ambient air requirements by the installation of double contact-
acid plants. If hydrometallurgy is to be a competitive technology it must in fact be so in
the marketplace with a clear and decisive edge. For this reason it would appear that
hydrometallurgy should not be viewed as a competitive technology but supplemental to
and in some cases compatible with smelting. In fact, lower energy versions of
hydrometallurgical processing of base metal sulfides often involve combined smelting
and hydrometallurgical applications.
1.3.0 Mineral Chemistry Electrochemistry

Hydrometallurgical extractions involve the interaction of the solid phase and an aqueous
phase in order to selectively dissolve the valuable metal. Thus an understanding of the
interphase interactions is essential.
1.3.1 The Electrode Electrolyte Interface

If two phases are places in contact, a region called the interface (interphase) is formed
between them. In this region a redistribution of electrical charge sometimes occurs in
which charge carrying particles pass from one phase to another, e.g. ions from a crystal
lattice of a metal or of a salt into solution and vice versa electrons from one metal into
another. Ions and dipole molecules may accumulate in the interface. When a metal is
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immersed in an electrolyte, an equilibrium tends to be established in which a potential
difference (p.d.) exist across the metal/solution interface. The origin of this equilibrium
p.d. lies in the atoms of the metal ionizing until the displacement of electrical charges
produced exactly balances the tendency for more metallic atoms to ionise:
M = Mz+ (aq) + ze- 1.1
The equilibrium constant will depend greatly on the metal and solution concerned.
E.g. Na, Cu, Pt in H2O
TASK: Elaborate this with respect to corrosion.

The electrode potential is confined to the close proximity of the interface because cation
loss by the metal leaves an excess of electrons which tends to orientate themselves
opposite a layer of cations of equal and opposite charge in the solution side of the
interface, such that a so called Electric Double Layer is established (or electric multilayer
in more refined models) The double layer is formed by attraction between ions of
opposite sign and repulsions between those of same sign. The effect of such disturbances
is to diffuse cations among anions throughout the bulk solution until equilibrium is not
only established across the metal/solution interface but between bulk and interfacial
solution. Particularly in dilute solutions, this may lead to an additional component of the
electric multilayer- the diffuse double layer.
1.3.2 Electrochemical Potential

The distribution equilibrium for uncharged particles (i) distributed between two phases,
assumes an equality of the chemical potentials () of this component (i) in the two
phases. [- measure of the work done in the reversible transfer of 1 mole of uncharged
particles from the inside of a given phase () into an infinitely dilute gaseous phase, that
by convention defines the zero of the chemical potential scale]
For the analogous transfer of 1mol of charged particles, work must be done to overcome
not only the chemical and dispersion forces, but also the electrical ones. The measure of
this work () is called the electrochemical potential and may be regarded as:
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i = i + ziFi 1.2
Where ziFi indicates electrostatic work associated with the infinitely slow transfer of
charge zF (Cmol-1) from an infinite distance in vacuum to the inside of a phase () with
potential i this inner or Galvanic potential may have two components:
An outer Volta (electrostatic) potential which is a long range term; If the phase
possesses excess electrical charge supplied from outside and
A short range surface potential term due to dipole orientation at the interface.
Illustrated by equation 1.3 below:
= + 1.3
Where is dipole orientation
1.3.3 Electrochemical cells

Such cells consist in their most elementary form of:
two electrodes which can either be metals or semi conductors and
an electrolyte which can either be an aqueous or organic solution, fused salt or
solid electrolyte with (one of ) two modes of operation possible:
With:
(i) Forward reaction is a galvanic cell
(ii) Reverse reaction is electrolytic cell
Examples:
i lead acid car battery (secondary or reversible cell):
PbO2 + Pb + H2SO4 = 2PbSO4 + 2H2O
ii Daniell Cell (primary):
Zn(s) + CuSO4 (aq) = Cu + ZnSO4
iii Leclanches (dry) cell:
Zn(s) + 2NH4Cl + MnO2 =Mn2O3 + Zn(NH3)2Cl2 + H2O
iv Chloro-alkali electrolytic cell:
2NaCl + 2H2O = Cl2 + NaOH + H2
v Aluminum electrometallurgical extraction:
Na3AlF6 + Al2O3 3NaAlOF2 + Al
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1.3.4 Uses of Electrochemical cells
(i) Source of electrical energy (batteries and fuel cells)
(ii) Source of thermodynamic information about cell reactions
(iii) Source of electrochemical data i.e. activities, transport numbers
(iv) Electrosynthesis of inorganic and organic chemicals
(v) Electrowinning and refining of metals
(vi) Electroplating, polishing, machining and forming
(vii) Effluent treatment
(viii) Electro-dialysis
(ix) Determination of electrochemical corrosion mechanisms
(x) Qualitative and quantitative electro-analysis
1.3.5 Notation
The composition of an electrochemical cell is shown schematically using chemical
symbols and vertical lines to denote phase boundaries. The potential difference at the
junction of two electrolytes, the so called diffusion or liquid junction potential is
indicated by a dashed vertical line, and in the ideal case where such a p.d. is eliminated
by a salt bridge the dashed line is replaced by two parallel vertical lines For example the
cell diagram for the Daniell cell is therefore written as:
-
Zn/ ZnSO4 (aq) // CuSO4 (aq)/Cu+
And the cell reaction by convention is written starting from the left, i.e. with the Zn
electrode:
Zn(s) + Cu2+(aq) = Zn2+(aq) + Cu(s)
The signs at the electrodes represent the charge accumulating on each one. As Cu is
nobler than Zn, Cu2+ ions tend to deposit making the Cu electrode positive. Such charge
is dispersed usually by an external electrical circuit in which electrons would flow from
the zinc to copper electrode.
The e.m.f. could be measured by matching it with an exactly equal and opposite e.m.f.
from a potentiometer, or by a digital volt meter with a very high input impedance (say >
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107 Ohm), such that negligible current is drawn. The cell e.m.f. (electromotive force-
potential under zero current conditions) will be a measure of the free energy change (G)
for the cell reaction(s), if the electrodes are truly reversible and if liquid junction
potentials are negligible.
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1.3.6 Liquid Junction potential
At the boundary between two electrolyte solutions with different chemical composition
concentration, concentration gradients are formed which cause the diffusion of individual
components in the transition layer. A diffusion potential gradient appears if the various
ions move with different rates.
Consider a junction between two solutions of a binary electrolyte such as HCl, present at
two different concentrations. Diffusion of the two types of ions from the stronger to the
weaker solution will take place at different rates, resulting in a p.d. being established
across the liquid junction, the faster ion being retarded and the slower one accelerated by
the direction of the field. If the concentrations of the two aqueous HCl solutions are c1
and c2, then the liquid junction potential is given by:
Ej = 0.0591(2t+ - 1) log (c1/c2) at 298k 1.4
So the cationic transport number is to 0.5, the smaller the liquid junction potential.
Aqueous HCl solutions have an unusually high value of (2t+ - 1), giving a potential of
39mV across the junction of 10-3M and 10-2M electrolytes. In similar circumstances, KCl
solutions give 1mV. With two different electrolytes the mathematical treatment is
complex, but for two univalent electrolytes at the same concentration and having a
common ion, the liquid junction potential is given by:
Ej = 2.303RT/Flog101/2 1.5
Where 1and 2 are the molar conductivities of the electrolytes at their respective
concentrations. Liquid junction potentials are an extremely common occurrence and may
render the measurement of electrode potentials ambiguous. To minimize their effect, a
salt bridge may be used to connect the two dissimilar solutions. This often consist of a
tube closed at both ends with porous material (or gel may be used), and filled with a
saturated solution of KCl, or NH4NO3 if Cl- has to be absent. Under these circumstances,
the (individual) liquid junction potentials are small as:
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(i) The bridge solution ions are present in excess over the ions in the electrode
components, so that charge transport across the junction is due almost
exclusively to the bridge ions.
(ii) The ionic mobilities of the anion and cation are approximately equal. The salt
bridge creates two liquid junction potentials opposed to one another, further
decreasing the resulting contribution to the total e.m.f.
A practically complete elimination of the liquid junction potential is allowed by the
addition (where/when possible) of excess indifferent electrolyte to each solution in the
electrochemical cell, so that almost all the charge transport across the boundary is due to
the indifferent electrolyte.
1.3.7 Types of individual electrodes
The overall cell reaction is due to the sum of two so called half Cell reactions taking
place at the two electrodes. According to IUPAC convention, such reactions are written
as reductions, i.e. electrons always appear on the LHS of the equation, and the cell e.mf.
is given by E (RHS) E (LHS) i.e. E (cathode) - E (anode). For the Daniell cell then, the
two half cell reactions are:
Cu2+ + 2e- = Cu : Eo = + 0.34V (vs. S.H.E.)
Zn2+ + 2e- = Zn : Eo = -0.765V (vs.S.H.E.)
Under standard conditions cell e.m.f. is: = 1.103V
As the individual potential differences (s) between metal (m ) and solution (s )
cannot be measured, each is determined with respect to a standard hydrogen electrode
(Pt/H2 (1 atm)/ H+ (aH+ =1)
The electrodes may be divided into three groups:
(i) Electrodes of the first kind
(a) Cationic electrode
metal/ metal electrodes, Mz+ + ze- = M
metal amalgam/metal ion electrodes, Mz+ + ze- = M(Hg)
the hydrogen (gas) electrode, 2H+ + 2e- = H2/Pt
At which equilibrium is established between the atoms of a metal and its cations in
solution.
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(b) Anionic electrodes e.g.
Oxygen gas electrode, gas-ion; Pt/O2 + 2H2O + 4e- = 4OH-
Chlorine electrode, Pt/Cl2 + 2e- = 2Cl-
Non metal- ion electrode, Pt/I2 + 2e- = 2I-
(ii) Electrodes of the second kind consist of three phases. The metal is covered
with a layer of its sparingly soluble salt and immersed in a solution containing
a soluble salt with the same anion. The equilibrium between the atoms of the
metal and anions in the solution is mediated by equilibrium with the insoluble
salt.
Example: (More practical reference electrodes than S.H.E.)
Ag/AgCl(s)/Cl-(aq); AgCl + e- = Ag + Cl-aq
Hg (l)/Hg2Cl2(s)/Cl-(aq); Hg2Cl2 + 2e- = 2Hg + 2Cl-aq
Hg (l)/Hg2SO4(s)/SO4 (aq); Hg2SO4 + 2e- = Hg + SO42-(aq)
1.3.8 Oxidation-Reduction (Redox) Electrodes

If an indifferent metal (most often Pt, sometimes Au or Hg) is immersed in a solution
containing a substance in two oxidation states. The common particles between the two
phases are electrons, their electrochemical potential being identical to the level in both
phases.
Examples:
Pt/Fe2+ (aq), Fe3+(aq); Fe3+ + e- = Fe3+
Pt/MnO-4(aq), Mn2+; MnO-4 + 8H+ + 5e- = Mn2+ + 4H2O
1.3.8.1 The hydrogen electrode and Standard electrode potentials

The reversible hydrogen electrode consist of a Pt wire or foil electrode coated with finely
divided Pt, electrodeposited from aqueous chloroplatic acid (H2PtCl6) to increase the
effective surface area several hundredfold. (Procedure for its preparation is in E.C.
Potters book, ref. p.101). This is immersed in a solution containing H+ ions (arsenic free
aqueous HCl) and saturated with (O2 and CO free) hydrogen gas, which is bubbled over
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the Pt surface. The two opposing reactions proceeding at the same rate at a reproducible
potential are then:
2H+ + 2e- = H2/Pt
Easily reducible organic, nitrates at very low pH,
The electrode surface is easily poisoned by As, Hg compounds ClO3-, MnO4-, CN-, S2-,
CO, and deposited metals and any colloidal systems which alter the equilibrium potential.
The required reversible hydrogen electrode potential (EH) is given by the Nernst equation
for the reaction:
EH = EoH + (RT/2F) loge (aH+) 2/aH2T 1.6
The potential is pH and H2 pressure dependent. When the activities aH+ and aH2 are unity
(1.2 M aqueous HCl and 1 atm. H2 gas respectively), then EH = EoH, the standard
electrode potential of the hydrogen which is by convention defined as zero at all
temperatures
At 298K therefore, the Nernst equation reduces to:
EH = 0.059 log aH+ = -0.0295log aH2 1.7
And at aH2 = 1,
EH = 0.059 log aH+ = -0.0295pH 1.8
Thus the electrode may be used to measure pH. However,
(i) The system is cumbersome and difficult to set up,
(ii) The response is not always good
(iii) Many solutions (poison) electrode, and some are reduced by it e.g. Ni (II).
The standard hydrogen electrode (SHE) [Pt/H2 (g), (atm.)/ H+(aq) (aH+ =1)],
Being arbitrarily defined (by I.U.P.A.C.) as of zero potential at all temperatures, is
used as the standard against which to compare the potentials of all other electrode
systems. This allows the tabulation of these electrode potentials as a scale from the
negative values of the very reducing/easily oxidized alkali metals (Li, Na, K, etc) to
the positive values of the very oxidizing/easily reduced systems (F2, Cl2, etc), known
as the electrochemical series.
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1.3.9 The e.m.f. of a Galvanic Cell
A galvanic cell is a system that can perform electrical work, when its energy is consumed
at the expanse of chemical or concentration changes that occur inside the system.
E.g. the Daniell Cell:
Cu (II) + Zn = Zn (II) + Cu
Such chemical changes may be performed reversibly only if there is both material and
energetic reversibility, so that most practical galvanic cells show some degree of
irreversibility. Material reversibility can be demonstrated by balancing the e.m.f. of the
cell with an equal and opposite p.d. from a potentiometer. Therefore causing the reaction
to proceed in one direction and then the other. By altering balancing p.d. to be less than
then greater than the cell e.m.f., and carrying out a material balance. Energetic
reversibility is achieved if, when the reaction occurs in one direction, the same amount of
electrical work is expended as is gained when the reaction proceeds to the same extent in
the opposite direction. In the reversible case the reaction proceeds infinitely slowly, the
free energy change for the cell (G) is transformed into an equivalent smaller and can be
zero (as in the case of a dead short, which is equivalent to a Zn electrode in Cu (II)
solution.
1.3.9.1 Rules applying to Galvanic Cells
(i) The non ionic material of the LHS electrode in the cell diagram must appear
on the LHS of the equation representing the reaction.
(ii) Cell e.m.f. = E(RHS) E(LHS)
(iii) Cells containing a hydrogen electrode must be written with that electrode on
the LHS
(iv) Half cell reactions are written as reduction reactions electrons always appear
to the LHS
Examples:
(i) Zn2+(aq) + 2e- = Zn(s)
(ii) AgCl(s) + e = Ag(s) + Cl-(aq)
Zn(s)/ZnCl2 (aq)/AgCl(s)/Ag(s)
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Cell reaction = half cell reaction (ii) (i)
I.e. Zn(s) + 2AgCl(s) = 2Ag(s) + ZnCl2 (aq)
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1.3.10 Thermodynamics of Electrochemical Cells
If the reaction: Zn(s) + CuSO4 (aq., 0.5M) ZnSO4 (aq., 0.5M) + Cu(s)
Is carried out as written, in a calorimeter at 188K, it is quite irreversible and a H
(reaction) = -235.2 KJmol-1 may be measured
However if the Daniell cell:
-
Zn/ZnSO4 (0.5M)// CuSO4 (0.5M)/Cu +
Is set up, the same reaction maybe carried out reversibly. The maximum work will be
done if the reaction is carried out infinitely slowly, i.e. the resistance across the cell R
approaches infinity and the current approaches infinity. The enthalpy change is given by:
H = qrev + Wmax 1.9
H = TS + Wmax(maximum electrical work) 1.10
TS for the reaction is -23.83kJmol-1, so that S = - 82.8Jmol-1k-1
From the definition of electrical potential, the work done when a charge q (coulombs)
passes between two points differing in electrical potential by V (volts), is qV (joules). In
an electrochemical cell, the maximum electrical work (Wmax) supplied to the
surroundings is given by:
Wmax = -charge x reversible cell potential (e.m.f.)
Given that:
G = - nFE 1.11
And if all the reactants and products are in their standard states
Go = - nFEo 1.12
These last two equations relate the free energy change (Jmol-1) for the cell reaction when
an equivalent charge nF(Cmol-1) of reactant is converted reversibly to product at the
reversible potential (e.m.f.) where n is the number of moles of electrons or equivalents
involved in the cell reaction and F is the Faraday constant (96487 Cmol-1) or the total
charge of 1 mol of electrons (Avogadro number 6.023 x 1023 charges/particle mo-11)
multiplied by the value of a single electronic charge (1.602 x 10-19 C))
From Gibbs Helmholtz equation,
(G)/ T = -S 1.13
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Substituting for G gives:
(-nFE)/ T = -S 1.14
S = nF (E/ T) 1.15
Where E/ T is the temperature coefficient of the cell e.m.f., which provides a simple
means of determining S for the cell reaction
Similarly, when all products and reactants are in the standard states
So = nF (Eo/ T) 1.16
As G = H - TS
H = G + TS 1.17
Substituting for the value of G in equation 1.17 gives:
H = - nFE + T nF.E/ T 1.18
H = nF (T (E/ T) E 1.19
Similarly, when all the products and reactants are in their standard states,
Ho = nF(T(Eo/ T) Eo) 1.20
The equilibrium constant (k) for the reaction is related to the free energy change (G) is
given by the equation:
G = -RT ln k 1.21
Substituting for G gives equation:
nFE = RT ln k 1.22
k = exp (nFE/RT) 1.23
I.e. equilibrium constant can be evaluated from the e.m.f. of an appropriate
electrochemical cell.
1.3.11 Variation of Electrochemical Cell E.m.f. with Activities
The e.m.f. of the cell:
Pt/H2(g)/ HCL(aq)/Hg2Cl2(s)/Hg(l)
Depends on PH2, aH+, aCl-
Cell reactions for the above cell is
H2 (g) + Hg2Cl2(s) = 2H+(aq) + 2Cl-(aq) + 2Hg(l)
G = G (products) - G (reactants)
G = 2Hg + 2H+ + 2Cl- -H2 -Hg2Cl2 1.24
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Where is the chemical potential or partial molar free energy
Now: i = i o RT ln ai
So that:
G = 2Hg + 2oH+ + 2oCl- + 2RT ln aH+ + 2RT ln aCl- -oH2 - RT ln aH2 -oHg2Cl2
G = Go + 2RT ln aH+ + 2RT ln aCl- - RT ln aH2 1.25
Substituting gives equation
E = Eo 2(RT/nF) ln( a2H+.aCl-) + RT/nF ln aH2 1.26
In general, for the reaction:
1/2H2 + oxidized states = Reduced states + H+
E = Eo + RT/nF ln(aoxidised states/areduced states) 1.27
This is one form of the Nernst equation
1.11.1 General Rules
write the most likely equation for the supposed reaction
Write down the cell for which this equation represent s the cell reaction
write down the electrode ( half cell) reactions which together give the cell reaction
Add algebraically the standard electrode potential values from the standard tables for
these systems which will give the standard e.m.f. of the cell
[Use the standard free energy changes for the component reactions]
Equate the E0 values (standard e.m.f.) obtained with (RT/nF)lnK.
Example:
(i) Calculate the solubility product of silver bromide
AgBr(s) = Ag+(aq) + Br-(aq)
Ag(s) /AgNO3(aq) // KBr(aq) /AgBr(s) /Ag(s)
Ag(s) + AgBr(s) = Ag+(aq) + Br-(aq) + Ag(s) (1)
H2(g) + Ag+(aq) = 2H+(aq) + 2Ag(s) (2)
H2 (g) + 2AgBr(s) = 2Ag + 2H+(aq) + 2Br-(aq) (3)
2 x reaction (1) = reaction (3) reaction (2)
2G(1)o = G(3)o - G(2)o
2n1F E1o = n3F E3o -n2F E2o
E1 o = E 3 o - E 2 o = - 0.728V
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Go = -2.303RTlog K
LogK = E1oF/2.303RT
K = 5.4 x 10-13 mol2dm-6
N.B. for small errors (say mVs) in t one of the standard electrode potential, large errors
will be incurred in the value of the equilibrium constant k, because of the logarithmic
calculation.
(ii) Calculate the thermodynamic solubility product (Ks) for the reaction:
AgCl(s) = Ag+(aq) + Cl-(aq)
Ks = (aAg+. aCl-)/ aAgCl
2
a AgCl = 2 (AgCl) . CAg+ .CCl-
where CAg+ .CCl- = S
log10Ks = 2log10 (AgCl) + log 10S 1.28
From the Debye- Hunkel limiting law:
2log = Az1z2I 1.29
Where I is thee solution ionic strength and z1z2 the ionic charges
log10Ks = -2 Az1z2I + log 10S 1.30
If the D_H law is valid, by measuring S at different ionic strengths and plotting log 10S
and I should yield a straight line of slope -2A and intercept = log10Ks.
1.3.12.1 Electrical Conductivity
Electrical conductors are characterized by their conductivity ( ohm-1mol-1) or resistivity
( = 1/ ohm m). These quantities are proportionality coefficients in the relation between
resistance (R) of a homogenous conductor, its length (L) and its cross sectional area (A)
1/R = .A/L = 1/ .A/L 1.31
The conductivity may be represented by the conductance of the material of length 1m and
cross sectional area 1mm2, the amount of current passing in the direction of length () is a
constant characteristic of the solid or pure liquid concerned, for solutions it depends on
the concentration.
In general = current density/electric field = I.L/A.V ohm-1m-1
Where V is the voltage drop over the length, I the total current flowing through the cross
sectional area (A)
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For electrolyte solutions, the molar conductivity = /c ohm-1mol-1m2 where c is the
electrolyte concentration molm-3 or ms (1ms = 10-3-1)
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Table 1.1 Materials and conductance
Conductor Charge Temperature Notes
type carrier effect
Metals electron negative Solid and liquid metal, graphite
coefficient
Non Electrons & Positive Non metallic oxides and sulphides,
conductors holes coefficient generally non stoichiometric
electrolyte ions positive Salts in water and solvents, fused salts.
coefficient Ions move in both directions
1.12.2 Electrolyte Solutions

Kohlauschs law of independent ionic migration: o =+o + _o
Where +o and _o are the molar ionic conductivities (ohm-1m2mol-1) of the cation and
anion of a 1:1 electrolyte at infinite dilution (as c approaches 0) , hence the superscript
zero, such that it may be assumed that there is no interaction between ions . +o , _o
The conductivities depend only on:
(a) the nature of the ion and not on the other ions
(b) temperature
(c) viscosity of the medium
Classification of Electrolytes
(a) Non associated (strong ) electrolytes
Only entities present in solution are anions and cations, possibly solvated.
Examples include, alkali, alkali earth metals and possibly solvated rare earth halides,
nitrates , perchlorate and some transitional metals halides in water, NaCl, MgBr2,
LiF3 etc. strong acids e.g. HCl, HI, HCLO4 are entirely ionised in fairly dilute
solutions e.g. H+(H2O)xClO4-
(b) Associated electrolytes
(i) Weak electrolytes systems where equilibrium exist between covalently
bonded molecules and free ions (possibly solvated). E.g. most acids (except
strong acids) and bases (except alkali metal hydroxides)
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(ii) Ion pair electrolytes- systems involving equilibrium between a loosely defined
aggregate of more than two ions held together supposedly by electrostatic
forces. E.g. all salts in non aqueous solvents, certain salts in water
Figure 1.1 shows relationship between conductance and concentration of electrolytes
Concentration Concentration
(a) Strong electrolyte (b) Weak electrolyte
Figure 1.1: Relationship between conductance and concentration of electrolyte.
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2.0 Leaching Technology
At the end of this section you are expected to:
Discuss the scope of leaching
Construct appropriate Eh/pH diagrams using data from standard booklets
Interpret thermodynamics data
Use thermodynamics and kinetics data to predict feasibility of leaching
Explain the shrinking core model and use it to predict leaching reactions
Distinguish the different leaching methods
Evaluate the benefits derived and challenges for each method
Select the appropriate leaching method for a given ore
Discuss the principles of biological leaching and justify its use in treating certain ores
2.1 Scope of Leaching Practice

Ore usually is transported from the mineral deposit for leaching. In some special cases
leaching may occur in situ but these examples are few and will be treated separately.
Normally, the ore is transported and treated by methods that depend on the value of the
ore. It is useful to consider three ore types:
Low-grade ore
Direct leaching ore
high-grade ore (suitable for beneficiation)
The major example of the leaching of a low-grade ore is in copper hydrometallurgy
commonly practiced in the western United States where copper is placed on vast leach
dumps and is treated by recycling leach solutions. These dumps contain both sulfides and
oxides of such low grade that they are not suitable for beneficiation. Leaching of dumps
extends into years and in the best leaching operation achieves approximately a 15-20%
ongoing or steady-state recovery of the new material content being placed on the dump.
Heap leaching usually refers to the leaching of oxides and is carried out on prepared
leaching pads, with leach cycles of days to months.
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Other minerals leached by heap-leaching technology include Uranium, gold, and silver
are also leached, though in relatively minor tonnages. Figure 2.1 shows the processing
routes of the three types of ore.
Figure 2.1: Various paths for handling ore in leaching practice
The second type of ore (direct-leaching ore) is one which has sufficient value that it can
be crushed or ground to appropriate sizes for vat leaching or agitation leaching. Examples
are copper, uranium, vanadium, gold, silver, aluminum, nickel, cobalt, and beryllium.
Pretreatment by oxidative, reductive, or salt roasting may be necessary to render the
material suitable for leaching.
High-grade ore is of sufficient value that it may be beneficiated to increase recovery and
produce a concentrate. The concentrates produced may be pretreated by roasting prior to
leaching. Each process produces leach liquor which must be treated by some separation
process for the recovery of metal values as metals or as salts requiring further treatment.
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The various leaching processes produce either a dilute process stream or concentrated
liquor. Low-grade ores invariably produce dilute process streams. For example, copper
dump-leaching effluents usually contain 0.5-1 g per liter of copper. In the case of direct-
leaching ore, the leach liquor may be either a dilute process stream requiring upgrading or
a concentrated stream requiring no additional upgrading. The leaching of concentrates
produces high grade liquor that can be sent directly to metal recovery by reduction or
precipitation.
2.2 Thermodynamics of Leaching
In covering this section, it is assumed that the basics of thermodynamics of leaching were
covered at diploma level; therefore it is recommended that you revise the fundamentals
covered then and build up on the concepts then covered. This section therefore will cover
Construction of Potential/pH (Eh/pH) diagrams which is one of the thermodynamics tools
used to help predict leachability of an ore.
2.2.1 Construction of Potential/pH Diagrams or Pourbaix Diagrams
The aluminum-water system is used to illustrate the construction:
Step 1
Select the relevant thermodynamics data relating to the appropriate equilibrium
Data at 25oC (298K)
Al3+ + 3e- = Al: Eo = -1.663V (1)
2Al3+ + 3H2O = Al2O3 + 6H+: log K = -11.4 (2)
- +
Al2O3 + H2O = 2AlO2 + 2H : log K = -29.2 (3)
Al2O3 + 6H+ + 6e- = 3H2O + 2Al: Eo = -1.55V (4)
AlO2- + 4H+ + 3e- = Al + 2H2O: Eo = -1.262V (5)
Step 2
Consider each equilibrium equation separately:
When considering leaching, an activity of 10-3 mol.kg-1 for all metal ionic species may be
considered to represent a significant concentration of the species in aqueous solution.
(a) Equilibrium (1) involves electrons, and the Nernst equation is applied
E = Eo+ RT/zF ln aAl3+
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Assuming aAl3+ = 10-3 mol.kg-1 and substituting numerical values for (z = 3, T = 298K)
Gives E = -1.722V
This is a constant potential line represented a horizontal line on the Eh/pH graph and it is
the equilibrium line showing the stability of Al and Al3+ phases. This equilibrium is
independent of pH
(b) Equilibrium (2) involves H+ but not electrons. An expression for the equilibrium
constant is K = a6H+/ a2Al3+.
Taking logarithms for both sides;
Log K = 6log aH+ -2log aAl3+
Rearranging and substituting for the values of log K and aAl3+
pH =2.9
This is constant pH line represented by a vertical line on the Eh/pH graph and it is the
equilibrium line showing the stability of Al3+ and Al2O3 phases. This equilibrium is
independent of potential.
(c) Equilibrium (3) involves H+ but not electrons and the expression for the equilibrium
constants is K = a2H+ x a2Al02-
Taking logarithms both sides and substituting for the numerical values of logK and
aAl02- (10-3 mol/kg)
pH = 11.6
This equilibrium is independent of potential and is thus represented by a vertical line, but
because the lower termination of the line is still to be determined, the value of the pH is
tentatively inserted in the diagram.
(d) Equilibrium (4) involve H+ ions and electrons and its consequently
E = Eo+ RT/zF ln a 6H+
This at 298k becomes
E = Eo+ (0.0591/z) log a 6H+
But pH = - log aH+
And substituting z =6, and Eo =-1.55V
E = -1.55 0.0591pH
Substituting for pH =11.6 gives -2,236V as the termination point for the line in (c) above.
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(e) Equilibrium (5) like (4) above is dependent on both the H+ ions and electrons thus
using the Nernst equation yields:
E = Eo+ RT/zF ln(a4H+ x aAl02-)
This at 288 K becomes:
E = Eo + (0.0591/z) log aAl02- + (0.0591/z) log a4H+
Substituting for pH, z =3, Eo= -1.262V and aAl02-= 10-3mol.kg-1

E = -1.321 -0.079pH
By substituting an appropriate pH in the equation the E/pH diagram is completed
Step 3
Superimpose the domain of thermodynamic stability of water on the diagram.
Task 1: Using this calculated information, Construct the Eh/pH diagram for the Al-H2O
system. Comment on the solubility of aluminum in water. Comment on how useful this
data is in predicting leaching of alumina.
Task 2: Using the same procedure, construct the Eh/pH diagram for the gold- water
system. What can you conclude on the solubility of gold in aqueous solutions?
2.3 Kinetics of Leaching

Most metal sulfides and certain metal oxides are electronic conductors and are capable of
establishing corrosion and galvanic couples in aqueous solutions. Similarly, metals react
by well-established kinetic patterns involving corrosion couples displaying charge
transfer or diffusion over voltages or combinations of these depending on the metal.
Metal sulfides and several important oxides display n-type or p-type semi-conducting or
metallic properties. As a result of their electronic conductivity, certain minerals can
participate in coupled charge transfer processes analogous to a metal corroding in an
electrolyte, and the kinetics of leaching can be related to the potential of the solid in
contact with the aqueous electrolyte. Electrochemical processes are unique in that the
solid assumes a uniform potential throughout, providing ohmic resistance is negligible.
Consequently, the chemical reaction may be influenced over relatively long distances.
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The potential may directly affect the kinetics of the reaction and may also serve to
stabilize intermediate solid phases. Concepts developed in the field of corrosion are
transferable to electron-conducting solids in hydrometallurgical systems. The mineral
particle behaves as an internally short-circuited (no external applied voltage) system
where the solid assumes a mixed potential determined by associated anodic and cathodic
processes. At the mixed potential, the sum of all anodic currents,
(2.1)
Where A is the electrode area and ia and ic are the anodic and cathodic current densities.
As in corrosion processes, two types of mixed-potential regimes may be operative:
corrosion and galvanic couples. The corrosion type involves a single phase having both
anodic and cathodic reactions on a single mineral surface.
2.3.1 Leaching of Matrix Ore Mineral
For purposes of clarifying the process a matrix model is used to illustrate the leaching
kinetics. In this section the treatment includes primarily the kinetics of single matrix-
block reactions exclusive of bulk flow parameters. Leaching of ore fragments involves
penetration of solution into the rock pore structure and thus kinetics involves diffusion of
lixiviant into the rock where reaction with individual mineral particles occurs. The
kinetics are however made complex by changing porosity, pH, and solution
concentration. For leaching involving a gaseous phase for example oxygen, diffusion of
oxygen and subsequent reaction with mineral particles combine to give a non-steady-state
concentration gradient within the ore fragment. This treatment provides a basis for
modeling of all similar leaching systems.
Figure 2.2 is used here to illustrate the shrinking-core concept which is a special l case of
the general treatment. It illustrates the mineral fragment, showing different regions at
some time. Oxygen and copper gradients vary markedly over a broad zone in which
chalcopyrite (Cp) particles extend from partly to totally reacted. The fragment,
considered as spherical, may be viewed in cross section, as divided into annular rings of
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thickness Ar. If J is the net total flux of dissolved reactant diffusing into and out of this
incremental volume, the continuity equation for an individual ore fragment is
(2.2)
Where e is porosity, C is concentration, t is time, A is the area at radius r, and (R is the
rate of loss of reactant per unit volume because of reaction with mineral particles.
Actually, this is a summation of rate processes for all mineral types and sizes, within the
incremental volume. The porosity must be included since only the solution volume is
involved. Combining Eq. (2.2) with Fick's diffusion equations gives
(2.3)
Where Deff is the effective diffusivity. The effective diffusivity is related to the intrinsic
diffusivity, D, by the equation
(2.4)
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Figure 2.2 Schematic drawing illustrating the leaching of a matrix mineral fragment
containing disseminated copper sulfide particles.
If the rate of reaction of individual mineral particles is fast enough, the region of partially
leached minerals (Fig. 2.2) is fairly narrow. Such a condition is illustrated in Fig. 2.3
where a reaction zone of thickness moves topochemically inward during the course of
the reaction. According to the reaction zone model, steady-state diffusion occurs through
the reacted outer region and is equal to the rate of reaction within the reaction zone itself.
Figure 2.3: Matrix mineral fragment illustrating reaction zone and unreacted zones
The effective area of mineral particles within the moving reaction zone is assumed to be
essentially constant and independent of the mineral particle-size distribution since new
particles in each size fraction will begin to leach at the leading edge of the reaction zone
just as similar particles are completely leached at the tail of the reaction zone. The rate of
reaction within the reaction zone may be expressed by the equation
(2.5)
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Where:
n = moles of leachable minerals
t = time
np = number of mineral particles per unit volume of rock
Ap = average area per particle in the reaction zone
k's = rate constant of mineral particle
Cx average concentration in the reaction zone
= geometric factor accounting for deviation from sphericity
Diffusion through pores to the reaction zone may be expressed by the equation
(2.6)
Where
KH = Henry constant
C = bulk solution concentration
Deff = is the effective diffusion coefficient
= stoichiometry factor (number of moles of reactant required per mole of metal
released).
Task: How does the matrix ore mineral model help to predict leaching of gold from its
ores? Given that generally the grades of ores differ, what could be the differences (if any)
predictable for high grade and low grade ores.
2.4 Leaching Practice

This section will review the common types of leaching processes, however it assumes
fundamentals would have been covered in the diploma course.
2.4.1 Leaching of Low-Grade Ores
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Approximately 12% of total copper production is attributed to dump leaching of low-
grade predominantly sulfide-waste materials. In copper dump leaching practice, waste
rock (usually below 0.2% copper) is placed on dumps by truck or rail haulage. These
dumps vary greatly in size and shape. Depths extend from a few tens of feet to as much as
1200 ft. It is generally recognized that good aeration is required as well as good
permeability. Consequently, the stepped surfaces in the dump are usually ripped to
provide needed permeability. As mined ore, newly placed on a dump, will have
permeability of approximately 1000 Darcys (*Darcy refers to hydraulic conductivity or
permeability. Permeability in cm/s is converted to darcys by multiplying by 1045). Weathering
and deposition of salts significantly affects permeability with time and these are essential
in assessing expected recoveries, since leaching may extend for years. The porosity of
newly dumped rock can be adversely affected by the weight of haulage trucks can cause
compaction and result in a reduction in porosity from 45% to as low as 25%. Thus recent
processes use stackers instead.
Figure 2.4 illustrates a dump cross section showing important hydrological and structural
characteristics.
Figure 2.4 Cross section of leach dump illustrating physical and hydrological features,
(Reproduced from Whiting)
2.4.1.1 Important Aspects of dump leaching
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1. Channeling. Channeling of leach liquor occurs as a result of compaction and salt
precipitation. Fluid flow down channels essentially bypasses regions of the dump. It is
enhanced if solution application is by surface ponding.
2. Seep or Blowout. Compacted zones may cause entrapment of solutions, resulting in the
formation of a perched water table within the dump. The buildup of hydrostatic pressure
can cause surface seepage and even expulsion of solid material from the dump wall.
3. Stratification. During the dumping of waste rock, the coarse material travels further
down the slope or the dump than the fine material, causing stratification. Without
appropriate ripping, stratification may affect the flow pattern within the dump.
4. Sorption. Solutions bearing dissolved metals may pass through regions containing non
gravitational water at lower concentrations. Trapping of metal values can occur by inward
diffusion into the pore structure of the rocks and into stagnant aqueous regions.
5. Aeration. Aeration is best near the face of the dump, providing optimal conditions of
temperature and bacterial activity. Aeration by convection through the dump is an
essential part of the leaching mechanism. In regions of high oxidation potential, iron is
oxidized by bacterial activity to the ferric state resulting in the precipitation of ferric
oxides and jarosites.
6. Seepage Losses. Seepage can occur through the foundation of the dump, although the
formation of salts and the presence of fines often keep this at a surprisingly low level.
Runoff waters may also recharge or dilute the percolating liquors through the foundation
of the dump.
In practice, dump leaching depends on sequence of processes. Within the dump three
conditions are essential for leaching to occur and continue. These are:
Effective air circulation
Good bacterial activity
Uniform solution contact with the particle
The major unknowns in dump leaching for any given dump are:
A knowledge of air circulation relative to the dump configuration
The hydrology in terms of channeling and bypass
The effect of fines and precipitated salts
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The effect of weathering as a function of time
Figure 2.5 illustrates the general flow of solution to the dump, to a holding basin, and to
copper extraction. Copper extraction is achieved either by cementation on de tinned scrap
iron as indicated or by solvent extraction using one of the LIX reagents for selective
removal of cupric ion from sulfate leach liquors. The general trend is toward solvent
extraction due to the high costs of iron scrap.
Figure 2.5 Flow of leach liquors in copper dump leaching

2.4.1.2 Lixiviant application
Of special importance is the method of solution application. The general methods
employed are:
1. Pond irrigation.
2. Trickle.
3. Low-pressure multiple sprays.
4. High-pressure single spray.
5. Well injection.
The trend in dump leaching is toward trickle leaching or sprays. In ponding, channeling
can cause excessive dilution with loss of control over effluent quality. Trickle leaching is
carried out by using a network of perforated PVC pipe. This system provides a more
gradual application of solutions and more uniform air and solution access to the dump.
Spraying, using low-pressure multiple sprays or high-pressure single sprays, also
provides uniform coverage. Spray systems may suffer excessive solution loss by
evaporation in areas having high evaporation rates. Both trickle and spray leaching suffer
in some areas where excessive ice formation may occur during winter months. In such
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cases more than one method of solution application may be needed. The last method is
injection down wells. This is the method used in uranium solution mining. Wells are
drilled on a grid pattern and lined with perforated pipe. Solution flow is controlled by
combined down-well and up-well pumping through a flooded formation. Percolation
leaching using this method for copper recovery suffers because uniform coverage is
difficult. Solutions move generally downward under free-flow conditions, requiring a
close network of injection wells for adequate coverage.
Task 1: Make a survey of the application of dump leaching in gold mining locally
discussing the operation variables. What are the major challenges faced by users of this
technology locally?
Task 2: Zimbabwe has since closed its sole copper producing mine (Mhangura Mine)
citing economic feasibility problems, by analyzing the process that was being used for the
extraction of copper at Mhangura and the economics of it. Could the use of heap leaching
for treating mined ore and the scavenging for value in the tails that were thrown away, be
solution for the decommissioned mine? Carry out your analysis and come up with a
recommendation document based on your findings.
2.4.2 Direct Leaching Ore

Direct-leaching ores are those having sufficient value that they can be sized and subjected
to leaching in stirred reactors (pachuca or agitation tanks) or by percolation (vat
leaching). Important examples of direct-leaching ores are:
bauxites treated by the Bayer process
gold ores suitable for slime leaching
nickel laterites for nickel and cobalt recovery
acid and base leaching of uranium ores
Gold leaching has experienced some important recent developments and is an excellent
example of oxidation leaching. An important development in gold leaching has been the
reintroduction of older technology in the form of the carbon-in-pulp process.
The following steps occur in the carbon-in-pulp process:
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The leaching step produces gold cyanide anion in solution which is adsorbed on an ion
exchange site on the surface of activated carbon. The surface-active site on the activated
carbon (C-OH) is depicted here as an ion-exchange site. The actual mechanism is still
uncertain. Hot caustic stripping produces a high-grade gold stream suitable for recovery
of gold by electrolysis. The flowsheet of the Homestake Mining Company carbon-in-
pulp process is illustrated in Fig. 2.6 The process permits the countercurrent flow of
activated carbon to leach liquor.
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Figure 2.6 Homestake Mining Company carbon-in-pulp process flowsheet
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The Bayer process has similarly experienced significant change in recent years. It is an
excellent example of large-scale, nonoxidative pressure leaching. Changes in Bayer
process technology have resulted mainly from the need to treat more refractory ores.
Bauxite ore types are important since the difficulty of digestion depends on the form of
the hydrated aluminum oxide present. Aluminum in bauxite usually exists in one of three
forms:
and in addition contains iron to variable degrees. Bauxite ores high in gibbsite are less
costly to treat because of the relative ease of dissolution of gibbsite. Bauxites containing
the monohydrated minerals in large quantity are more difficult to leach, require higher
temperatures and pressure for complete digestion, and are more costly to treat.
Consequently, bauxites may be classified as low cost or high cost. Although the majority
of the bauxite processed is low cost (high gibbsite), this type is estimated to constitute
only 12% of total bauxite reserves.
The Bayer process involves the following steps:
1. Non oxidative dissolution of hydrated aluminum minerals.
2. Solid-liquid separation to remove ferric oxide, silica, and silicates.
3. Cooling, seeding, and precipitation of gibbsite, Al(OH)3.
4. Calcining of gibbsite to produce pure Al2O3
The chemical reactions involved in dissolution are

Al(OH)3 + NaOH = Al(OH)-4 + Na+
AlOOH + NaOH + H2O = Al(OH)4- + Na+
Ores containing essentially pure gibbsite may be digested at temperatures of 1500C while
boehmitic ores require temperatures in the range of 230-25O0C. These temperatures
reflect the differences in the solubility of the various hydrated aluminum minerals.
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Leaching of Nickel laterites represents another important example of direct-leaching ores.
The process involves the use of ammonium carbonate leach solutions for the dissolution
of an iron-nickel alloy produced in a reductive roast pretreatment step. The leaching takes
place at atmospheric pressure with oxygenation by air. An alternate process employs
sulfuric-acid pressure leaching of contained NiO and is suitable for low-acid-consuming
ores. Other direct leaching ores are given in Table 2.1 below.
Table 2.1 Direct leaching ores, indicating general methods of treatment
2.4.3 Leaching of High Grade Ores
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High-grade ores are those which may be economically beneficiated to produce a
concentrate prior to leaching. Examples of such concentrates are iron-nickel sulfide in the
case of the Sherritt Gordon Process, roasted zinc sulfide concentrates, standard in the
roast-leach-electrowinning practice for zinc recovery, zinc sulfides in the case of the new
Sherritt Gordon Cominco pressure leaching process, and flotation and gravity
concentrates for gold recovery by cyanidation. Recovery of gold from concentrates and
roast-leach electrowinning applied to zinc represent commercial processes used
throughout the world.
Figure 2.7 Simplified flowsheet for recovery of uranium by acid leaching

The application of hydrometallurgy to the treatment of conventional base metal sulfide
concentrates has not emerged as a promising new technology. Even if various smelter
sulfide intermediates are included as feed materials, the total number of plants treating
such materials remains few in number. The Sherritt Gordon process is historically
important as the first commercial application of hydrometallurgy to the recovery of nickel
from sulfide concentrates. The primary mineral is pentlandite, (Fe, Ni)S, associated with
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pyrrhotite, Fe12S11. The concentrate contains approximately 10% nickel and is treated by
pressure, autoclave leaching using air as the oxidant. Leaching is based on the formation
of soluble amine complexes of the form (Me(NH3)x)n+, where Me may be Ni, Co, Cu, Zn,
or Fe(II). The steps in the process are:
Leaching
Copper removal
Oxidation and hydrolysis of soluble sulfur intermediates
Nickel reduction using gaseous hydrogen.
The effluent aqueous stream is treated for cobalt recovery. Leaching is carried out in two
stages with excellent recoveries under the conditions 344-360 K (160- 19O0F) and
6.9 x 105 - l x 106 N/m2 (100-150 psig). The leaching reactions are:
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Figure 2.8 Sherritt Gordon pressure leaching process for recovery of nickel from nickel
concentrates
2.4.4 In Situ Leaching or Solution Mining
Recently, in-place (in situ) leaching of ore deposits has received increased emphasis and
appears to be an area in which significant advances will be made in the future. This type
of hydrometallurgical operation is often referred to as solution mining. It is useful to
consider dump leaching as part of solution mining since the physical and chemical
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features are similar to the leaching of fragmented or rubblized deposits in place. Much of
what is to be expected from in situ extraction can be derived from current experience and
practice in dump leaching. Deposits amenable to in situ leaching may be classified into
the three general groupings shown in Fig.2.9 are:
Surface dumps or deposits having one or more sides exposed, and deposits within
the earth's crust but above the natural water table.
Deposits located below the natural water table but accessible by conventional
mining or well flooding techniques.
Deposits below the natural water table and too deep for economic mining by
conventional methods.
Figure 2.9 Three generalized conditions for solution mining in situ

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Dump leaching is placed in the first classification. Type II is characteristic of what is to
be expected in the near future. Type III is expected to develop more slowly. Type I would
be the leaching of a fractured ore body near the surface above the natural water table in
the surrounding area. This would apply to mined out regions of old mines such as a
block-caved portion of a copper mine, or regions which have been fractured by hydro
fracturing or by the use of explosives. The chemistry and physical requirements would be
essentially the same as in dump leaching. Type II refers to the leaching of deposits that
exist at relatively shallow depths, less than approximately 500 ft, and that are under the
water table. Such deposits will have to be fractured in place and dewatered so they may
be subjected to alternate oxidation and leach cycles or percolation leaching, although the
use of special oxidants may eliminate the drainage cycle. This is a special problem
requiring a complete knowledge of the hydrology of the region. Water in the deposit, if
removed during the oxidation cycle, must be processed, stored, and returned under
carefully controlled conditions. An alternate method of leaching would be by flooding as
described for Type III below. An important, rapidly developing example of Type II is the
application of flooding using wells distributed on a grid such as is currently used for
uranium extraction. The third general type (Type III) of solution mining is represented by
deep deposits below the water table and below approximately 500 ft in depth. The ore
body is shattered, hydro fractured, or chemically penetrated. Again, the hydrology of the
region must be well known for proper containment of solutions. This represents a unique
situation in that the hydrostatic head will increase the oxygen solubility to the point that
the direct oxygen oxidation of sulfide minerals becomes possible.
Task: The geological section of your mining company has discovered a new ore deposit,
it is suggested solution mining is the most probable method of extracting the valuable ore.
As the process metallurgist you are required to appraise the use of solution mining for
this particular deposit. Explain what considerations you would have to carry out and what
would be your basis of recommending in situ leaching.
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2.4.5 Biological Leaching
In nature sulfide ores are decayed by weathering under the influence of oxygen and
water. Microbiological investigations reveal that certain bacteria are the main agent in
this process. Several bacteria, especially Thiobacilli, are able to solubilise any heavy
metal minerals by oxidizing ferrous to ferric iron as well as elemental sulfur, sulfides and
other sulfur compounds to sulfate. So they enhance leaching of heavy metals from sulfide
ores under aerobic conditions about 104 fold or more compared with weathering without
bacteria.
The principal bacterium in ore leaching is Thiobacillus ferrooxidans, which is capable of
oxidizing ferrous iron as well as sulfur and sulfur compounds. But there are some other
bacteria which may also be involved. For example the thermophilic Sulfolobus plays a
role in leaching at elevated temperatures. Thiobacillus thiooxidans, which oxidizes
merely sulfur and sulfur compounds but not iron, and Leptospirillum ferrooxidans, which
contrarily oxidizes ferrous iron, may play a role if they work together or with other
bacteria. Basic microbiological research focuses on the biochemistry, physiology and
genetics of the involved microorganisms and on the complex interrelationships in the
microbial community of leaching biotopes.
Microbial leaching of ores depends primarily on bacterial processes which are the
essential causes of natural weathering of sulfidic minerals. If sulfidic heavy metal
minerals come into contact with air and water they begin to decay with the formation of
sulfate, sometimes sulfuric acid, and water soluble heavy metal cations. Figure 2.10
shows an outline of bacteria leaching.
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Figure 2.10 Bacteria leaching process network
2.4.5.1 Thiobacilli
These are the principal bacteria which play the most important role in solubilising sulfidic
metal minerals at moderate temperatures. Most species are tolerant to acids and, and
acidophilic. Some grow best at pH ranges between 2 and 0.5 and most species are also
tolerant against heavy metal toxicity.
Thiobacilli are chemolithoautotrophs, (that means CO2 may be the only source of carbon
and they derive their energy from a chemical transformation of organic matter). All
Thiobacilli oxidize sulfur or sulfur compounds to sulfate or sulfuric acid. If they oxidize
hydrogen sulfide, thiosulfate, polythionates or elemental sulfur they produce hydrogen
ions and so they lower the pH of the medium, often below pH 2.
HS- +2O2---SO42- + H+
So +H2O + 1.5O2 a SO42-+ 2H+
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2.4.5.1.1 Thiobacillus ferrooxidans
Normally, the oxidation of ferrous iron to ferric is slow. The bacterium Thiobacillus
ferrooxidans, an aerobic chemoautotroph deriving its energy from the oxidation of
ferrous iron, greatly accelerates the oxidation of ferrous iron according to the following
reaction:
Oxygen is essential to the metabolic cycle of the bacteria. The bacterium Thiobacillus
thiooxidans is also an aerobic chemoautotroph deriving its energy from the oxidation of
elemental sulfur, thiosulfate, or sulfide as contained in heavy metal sulfides. Sulfur
oxidation produces sulfuric acid in place, an essential feature in maintaining open
porosity in dump leaching. Pyrite is a strong acid producer, supplying ferrous iron which
is subsequently oxidized to the ferric state in the presence of ferrooxidans. Pyrite also
greatly influences the net consumption of oxygen in the system which often may be as
high as 7-20 moles of oxygen per mole of Cu2+ produced. Ferric iron in solution exists in
several forms. The more important forms are Fe(SO)2-, FeSO4+,
Fe2(OH)22+, and FeOH2+. The sulfate complexes are greatly favored over the hydroxyl
complexes. To illustrate the importance of iron complex formation, a typical leach
solution will be considered in equilibrium with precipitated hydrogen jarosite, having an
approximate free-sulfate activity of 0.02. The equilibrium is represented by:
For which log K = -2.7. The iron sulfate complex equilibriums are
And
With log K values of 4.15 and 5.4, respectively. In the total dump-leaching system, the
oxidation sequence is:
1. Aeration by convection, promoting bacterial activity.
2. Oxidation of ferrous iron to ferric.
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3. Ferric iron dissolution of sulfides with metal release and acid generation.
The dissolution reactions typically of importance in copper dump leaching are:
In addition to the oxidation of sulfur and sulfur compounds Thiobacillus ferrooxidans is

able to oxidize ferrous (Fe (II)) to ferric (Fe (III)) iron and so derive its energy from this
reaction. In this reaction hydrogen ions are consumed and so the pH of the medium
should rise. But at pH values higher than 2 the ferric iron precipitates as ferric hydroxide,
jarosites or similar compounds and this result in the formation of hydroxide ions, so that
the pH of the medium is lowered as is the case with the oxidation of sulfur compounds:
2Fe++ + 2H+ + O2 = Fe+++ + H2O

2Fe+++ + 6H2O = 2Fe(OH)3 + 6H+
2 Fe++ + 5H2O + O2 = 2Fe(OH)3 + 4H+
Thiobacillus ferrooxidans is the principal agent of bacterial ore leaching at moderate
temperatures.
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2.4.5.2 Other Types of Bacteria
In addition to thiobacilli there are some other bacteria known to be effective in
solubilzing sulfidic minerals. In hot biotopes containing sulfur or oxidizable sulfur
compounds, such as hydrothermal vents and self heating brown coal dumps one can find
sulfolobus. Like thiobacillus it is acidophilic, chemolithoautotrophic and derives its
energy from oxidation of sulfur and sulfur compounds and from oxidation of ferrous iron
like thiobacillus ferrooxidans. Its pH range is between 1 and 6. It is thermophilic with a
growth range of 45-85 degrees celsius and its optimum temperature is 75 degrees celsius.
This is the main agent of metal leaching at high temperatures.
2.4.5.2.1 Leptospirillum
This type of bacteria is chemolithoautotrophic, deriving its energy from oxidizing ferrous
iron like Thiobacillus ferrooxidans. However it is not able to oxidize sulfur or sulfur
compounds and is incapable of utilizing the iron of sulfidic minerals. Leptospirillum
ferrooxidans alone cannot solubilize sulfidic ferrous iron containing minerals. But in
cooperation with Thiobacillus thiooxidans, which is also unable to dissolve sulfidic
minerals, they can disintegrate sulfidic ferrous iron containing minerals by oxidizing and
bringing them into solution.
Task 1: Explain the significance of biological leaching in hydrometallurgical operations.
How do bacteria leaching in uranium extraction differ from bacteria leaching in
extraction of gold from sulfide ores?
Task 2: The Kwekwe roasting plant tailings are still rich in gold but conventional
leaching has failed to recover the value, however panners have through some
unconventional means been able to recover some gold. Could bacteria leaching be used to
recover the value? Explain. What challenges could be encountered in recovering this
value?
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3.0 Ion Exchange Processes
At the end of the section you should be able to:
Describe the mechanisms of ion exchange processes
Distinguish the different types of resins and explain their applications
Use the various efficiency measuring techniques to evaluate the efficiency of ion
exchange processes
Explain and analyse application of ion exchange in extraction uranium, base metals
and PGMs
Discuss recent developments in the use of ion exchange resins
3.1 Introduction
Leaching processes are rarely if ever completely selective, consequently the resulting
pregnant leach solutions contain impurities and often require purification prior to the
recovery of the sought metals. Ion exchange is one of the essentially chemical separation
techniques that can be utilized to provide enrichment as well as purification. Benefits of
enrichment of dilute solutions include:
Smaller volumes are handled
Lower capital equipment cost
Effective metal recovery
3.2 Ion Exchange processes utilizing solid resins
Ion exchange is used for separating cations in solution. Ion exchange materials are
naturally occurring silicates or synthetic resins- cross linked polymers (e.g. polystyrene),
onto which ions are attached. A cation exchange resin has anions attached (e.g. SO3-) and
allows exchange and hence separation of ions through a tube or column containing the
ion exchange material in the form of beads suspended in a suitable solution. A cation
exchange resin is often converted to the acid form (R X-H+) by mixing with an acid
before use. In the presence of metal ions, the resin exchanges cations:
RX-H+ + Na+ RX-Na+ + H+
And the metal ions become more are less strongly attached to the resin. Each ion can then
be eluted (washed off) in turn using suitable solvents such as citric acid solution which
complexes the rare earth metals. Those ions least strongly attached will be removed first
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and the others later. Ion exchange forms the basis of Ion exchange chromatography
used for quantitative analysis for water softening (Ca2+ Ions are exchanged for Na+
Ions) for the deionising of water (anions and cations exchanged for OH- and H+
respectively which react to give water ) and for the extraction of certain metal.
Synthetic Ion exchange resins are based on the condensation polymerisation of phenols
with formaldehyde. Sulphonation with H2SO4 introduces a strong acid functional group
SO3H. All acid inorganic groups produce cation exchange resins. Weak acid cation
exchange resins may be prepared by the introduction of a weak-acid functional group
on to a polystyrene network e.g. phosphoric acid (PO3H2) or carboxylic acid (COOH)
For anionic exchange resins an amine group is attached to the cross-linked polystyrene
network via an intermediate chloromethylation reaction. A strong base functional group
results when a tertiary amine is used, whereas a secondary amine produces a weak base
functional group.
3.3 General properties of polystyrene Ion exchange resins
High stability to solution temperature (strong acid cation exchange resins operate
at temperatures <120oC, but strong-base anion exchange resins operate at
temperature < 40 oC.
High stability towards chemicals and solvents generally, although strong oxidants
(e.g. HNO3, KMNO4) may cause some breakdown.
Only one type of functional group present.
Degree of cross-linkage can be controlled by the proportion of divinyl benzene
employed in the preparation.
3.4 Ion Exchange Process Description
Ion exchange is the reversible interchange of ion between an insoluble solid organic
phase and an aqueous phase
The ion exchange process consists of two steps
1) SORPTION
This is passing a solution containing the value metals through a resin bed. The value
metals ion transfer from the aqueous phase to the organic (resin) phase. Bed (resin)
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saturation is detected by the appearance of value metal ions in the efficient; at this stage
pumping must be stopped. The process is operated on a batch scale.
2) ELUTION
This is washing the loaded resin with a much smaller volume of suitable aqueous solution
to remove the value metal ions. Ion exchange is carried out under equilibrium conditions
for given solution volume, shaken with given weight of resin till equilibrium is reached.
In this case uptake of value metal species on the resin is characterized by the distribution
factor, D
D = concentration of metal ions in organic phase
concentration of metal ions in aqueous phase
3.5 Ion Exchangers
An ion exchanger is a framework a matrix which carries a positive or negative charge.
These are compensated by counter ions of opposite charge. Counter ions have the same
charge as those on the matrix. These counter ions are mobile and replaceable. A positive
charged matrix is an anion exchanger that is the counter ions will be negative. A
negatively charged matrix is a cation exchanger i.e. the counter ions will be positive. The
SPONGE MODEL is widely used to represent the action of ion exchange resins. The
model compares the ion exchanger to a sponge with counter ions in pores. When the
sponge is immersed in a solution it releases the counter ions into solution.
To preserve a charge balance in the sponge a stoichiometric number of ions from the
solution occupies the pores.
3.6 Characteristics of Ion exchange resins
The main properties that govern resin performance are:
i. Selectivity coefficient
ii. Separation factor.
iii. Ion exchange
iv. Breakthrough capacity
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3.6.1 Selectivity Coefficient
There are physical and chemical reasons why ion exchangers preferentially attract an ion
from solution in place of its counter ions. Selectivity coefficient is the thermodynamic
equilibrium constant for an ion exchange reaction of the type.
A+ + BR = B+ + AR
The selectivity coefficient (K) is given by:
K = [AR][B+]/[BR][A+]
The coefficient defines two characteristics of the resin:
(a) Exchange of equivalent amounts of ions.
(b) Preferential intake of an ion over another is by K:
K = [AR]/[BR]
This gives ratio of A+ and B+ in the resin phase which is in equilibrium with aqueous
[A+] and [B+]
Where
K=1; it shows that resin has no preference for A+ over B+
K>>1; shows that separation is easy.
If K is too high, it can lead to problems during elution and regeneration.
K - Must be determined for each particular operation.
2.6.1.1 Separation Factor ()

The affinity of metal ions for an ion exchange resin may be expressed alternatively by the
distribution coefficient.
Distribution coefficient (d) = Mass of metal per g resin
Mass of metal per cm3 aqueous solution
Distribution coefficients for two metals may be compared and the ratio dB/dA = the
separation factor (). The separation factor is thus an expression for the selectivity of one
ion relative to another and is analogous to the selectivity coefficient.
3.6 .2 Ion Exchange Isotherm
Its a plot of the equivalent ionic fraction in solution XA against equivalent ionic fraction
of the same ions in the resin phase YA.
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1.0
B
YA
(1)
(2)
(3)
0 1.0
Ionic fraction of A in solution, XA
Figure 3.2: Ion Exchange isotherm
Ion exchange isotherm is the most useful way of expressing equilibrium behavior in ion
exchange:
Curve (1) favorable equilibrium for the adsorption of B and the resin in preference to A
Curve (3) represents the reverse of (1).
Curve (2) resin shows no preference of either species.
3.6.3 Breakthrough Capacity
Breakthrough capacity is defined as the quantity of ions that can be taken up by the resin
column under given conditions before leakage occurs into the efficient. It is determined
from breakthrough curves. A breakthrough curve is obtained by monitoring the metal ion
concentration in the effluent during the sorption step and plotting this as a ratio of the
influent metal concentration against the volume of influent solution passing through the
column against the quantity of metal ions it contains.
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1.0
Breakthrough
capacity
C/Co
C
A
Milli equivalents of ions through the resin column
Figure 3.2: Sorption breakthrough curves

Figure 3.2 shows a series of breakthrough curves exhibiting decreasing flow rate (A-C)
Decreasing flow rate results in a steeper curve and a higher breakthrough capacity.
Only for an infinitely slow rate (curve C) would the breakthrough capacity be identical to
the total capacity, where total capacity is an expression of the total number of exchange
groups it contains in terms of ion equivalents. It should be noted that the point of
inflexion of a breakthrough curve denotes the total capacity.
3.7 Elution or Regeneration

Adsorbed ions are displaced from the resin by passing an excess of an electrolyte termed
the regenerant or eluant through the resin column. A plot of metal ion concentration
versus the volume of solution leaving the column; the eluant, is referred to as the elution
curve. Eluting agents commonly employed include acids, bases and complexing agents.
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3.8 Hydrometallurgical Applications of IER (Ion exchange resins)
IER finds vast applications in the processing industry and in hydrometallurgical processes
ion exchange is particularly suitable for high-cost, low-throughput purification processes.
Separately, the recovery of trace amounts of metal from effluent and waste streams
accounts for many applications, for example, chromium from spent metal plating
solutions and copper and zinc from wastes arising in the rayon and synthetic fiber
industry. However, the largest single application in hydrometallurgy is the recovery and
concentration of uranium from naturally occurring mineral ore bodies. At the present time
there is a recession in uranium demand and worldwide production is at a low level.
The most cost effective recovery processes involve the separation of uranium as a by-
product of other minerals or metals. Typical examples are the recovery of by-product
uranium from gold and the recovery of uranium during the refining of wet process
phosphoric acid. Fixed-bed ion-exchange plants were installed to meet the early demand
for uranium in the nuclear industry, although more recently liquid extraction using liquid
ion exchange reagents has found acceptance in some mining locations. Uranium plants
are typically capable of processing 100-1000 m3/h of pregnant solution and it is the
uranium industry that has been responsible for many innovations that have occurred in
the development of ion-exchange technology in recent years. The foremost equipment
development is continuous countercurrent ion exchange in multistage fluidized beds. This
novel technology has been advanced most vigorously in South Africa and several large
plants have already been erected. Ion exchange is particularly advantageous for the
treatment of low-grade uranium ore deposits. A typical example of one such application
is the Rossing uranium mine in Namibia shown in figure 3.3.
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Figure 3.3: Simplified flowsheet of uranium recovery circuit at the Rossing Uranium
Mine in Namibia
Continuous ion exchange also facilitates the separation of metals in high-concentration
aqueous solutions. A process was developed in South Africa to recover spent
hydrochloric acid from pickle liquors. The Metsep process used three continuous
countercurrent fluidized-bed columns to separate zinc and iron (Fe2+) in hydrochloric acid
prior to recovery in a pyrohydrolysis reactor. The flowsheet for the process is given in
Figs. 3.4 and 3.5 Separation is possible with feed streams containing about 20 g/L zinc,
120 g/L iron, and 30 g/L hydrochloric acid. A special weak base anion-exchange resin
was used with a specific gravity of about 1.2 g/cm3. This was vital, since the feed solution
density was about 1.1 g/cm3. Selective separation of the chloride complexes of Zn2+ and
Fe2+ is relatively easy since the latter does not form stable anion complexes at low acid
concentration. The removal of zinc from the acid stream is achieved by ion exchange and
this can be recovered subsequently by liquid extraction using a cationic extractant (di-2-
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ethyl hexyl phosphoric acid), thereby converting zinc chloride to zinc sulfate as a
fertilizer additive.
Figure 3.4 Flowsheet of the Metsep ion exchange plant in South Africa
3.9 Recent Developments in IER

There is a growing interest in the development of selective polymers for application in a
wide range of specialty operations ranging from the recovery of trace uranium in
seawater to the separation and purification of the platinum group metals in
hydrometallurgy. Research and development is most exhaustive in hydrometallurgy,
especially in the field of precious metals recovery, platinum group metals separation, and
base metal recovery.
It is interesting to note that separations in the first-row transition metals have been
achieved with selective liquid extractants consisting of nitrogen- and oxygen-containing
ligands, for example, hydroxyoximes. However, these elements will form weak anionic
complexes, especially in chloride media, and this is also true of the second and third-row
transition metals; such characteristics make it possible to carry out separations among the
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precious metals, that is, gold and silver, and the platinum group metals. There is a
considerable economic incentive to develop solid-phase ion-exchange processes for the
recovery of precious or alternatively toxic metals, such as mercury, from low-grade dilute
solutions. Selective Chelating polymers containing oxygen, nitrogen, phosphorus, and
sulfur ligands include:
3.9.1 Chelating resins with nitrogen-containing pendant groups
Tertiary and quaternary polymeric amines are effective for some specialty separation
processes the most notable being the recovery of uranyl sulfate or uranyl carbonate from
acid or alkali leach solutions. Some selectivity is also found among the first-row
transition-metal chloride complexes. The incorporation of a chelating ethylene amine
group(NH-CH2-CH2-NH) 2 increases markedly the stability of the polymeric ligand-
metal complex. For example, cross linked chioromethylated styrene divinylbenzene
copolymers containing di, tri, or tetraethylene amine groups show high affinity for
Au(III), Hg(II), and Cu(II).
3.9.2 Chelating resins with nitrogen- and oxygen-containing pendant groups
Amino-diacetic acid ion-exchange resins have been available for commercial use since
the early 1960s. Resins of this type are useful for the separation of the first-row transition
metals, although the selectivity is very dependent on pH. More recently, attempts have
been made to synthesize more elegant polymer supports and ligands. Many workers have
proposed chelating ligands based on poly(vinylimidazole) or poly(vinylimidazole)
dicarboxylate groups. It has been suggested that the loading rates for base metals, Cu(II),
Ni(II), and Co(II) are enhanced with this type of structural modification.
Amidoxime-type functional groups are found to chelate uranium at low concentrations in
seawater and to offer a potential solution to the problem of separating heavy metals from
acidic solutions.
3.9.3 Chelating resins with sulfur-containing pendant groups
Sulfur ligands are known to complex or precipitate most of the heavy transition metals.
Early developments in this field arose out of pollution control and analytical applications.
Typical polymer derivatives are based on macroreticular polymethacrylate beads
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containing pendant mercapto groups. Such resins are reactive for Ag(I), Hg(II), and
Au(III). Thioglycolate resins have been developed and used for the laboratory separation
of Ag(I), Bi(III), Sn(IV), Sb(III), Hg(II), Cd(II), Pb(II), and U(VI). Similar resins are
dithiocarbamates and their derivatives. Recently, the platinum group metals (PGMs) have
been separated in chloride media using a combined ion-exchange and liquid-liquid
extraction process. The adsorption step involves a weak base isothiouronium group
capable of extracting the chlorocomplexes of the PGMs. Industrial exploitation of this
technique has occurred already.
3.9.4 Chelating resins with phosphorus-containing pendant groups
Phosphoric acid, esters, and phosphate oxides are very effective extractants for uranium,
gold, and the first-row transition metals. One commercially available chelating resin
contains amino phosphoric groups attached to a cross linked polystyrene matrix.
Although developed for the decalcification of brines, this resin shows high selectivity for
the separation of trace amounts of uranium in wet process phosphoric acid.
3.9.5 Chelating resins with oxygen-containing pendant groups and macrocyclic
structures
Phenolic ion exchangers derived from a phenol-formaldehyde condensation reaction
appeared in the first generation of ion-exchange polymers. More recently, styrene-
divinylbenzene copolymers incorporating azo-substituted cresol and salicylic acid,
catechol, hydroquinone, and benzoquinone have been described. The quinone-type
polymers selectively sorb Hg (III) and the catechol resins sorb Cr (VI).
Task:
Zimbabwe is loosing a lot of capital by selling unprocessed minerals to other nations.
What is your opinion? Defend your opinion with reference to any local mine. How can
Ion exchange assist in value addition of these minerals? Using knowledge so far obtained
and literature, propose a design to process the minerals using IER which would lead to
value addition.
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4.0 Solvent Extraction Processes
Describe the mechanisms of solvent extraction
Distinguish the various solvent extractants
Explain the kinetics of solvent extraction using the two-film theory
Given a feed stream, design a solvent extraction process flowsheet.
4.1 Introduction
The solvent extraction process is based on the ability of a solute to dissolve in two
immiscible liquids. The equilibrium of the solute between the two immiscible solvents
can be defined in terms of the partition law which may be stated as follows:
A solute will distribute itself between two immiscible solvents until at equilibrium the
ratio of the activities of the solute in the two liquids is constant at any given temperature,
irrespective of the absolute value of the activities.
The ratio of the activity values in the two solvents is called the partition constant (Po) and
it depends on the nature of the solvents, and the temperature. If A and B are the solvents
and the activities of the solute are aA and aB respectively then;
Po = (aA /aB)
In hydrometallurgical assays where the concentration of a metal in each solvent is
important, the ratio of the metal concentration in the organic solvent to the metal
concentration in the aqueous solvent (D) is considered.
D = [M]o
[M]aq
Consequently, when the a volume Vo of organic solvent is equilibrated with volume Vaq
of the metal rich aqueous phase, the fraction of the metal extracted into the organic phase
is given by;
R = D
D+(Vaq/Vo)
Where R, known as the recovery factor, may also be expressed as a percentage.
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Metals exist in aqueous solutions generally as ions, e.g. Al(H2O)63+ . The presence of the
solvating water molecules increases the similarity between the ionic solvent and the
solute. In contrast, organic solvents are covalent in nature-giving rise to little or no
interaction with the ionic metal. For extraction to take place the metal must change to a
form compatible with the organic solvent through one of the following ways;
(i) charge neutralization
(ii) replacement of the solvating water molecules by covalent type ligands.
4.2 Extraction Mechanisms
There are basically three mechanisms by which the metal ions are rendered soluble to the
organic phase:
4.2.1 By the formation of uncharged coordination compounds

The most important group of coordination compounds for solvent extraction is the
chelates. These are reagents having at least two ligand atoms in the molecule and thus
give rise to ring formation. Uncharged chelates with five or six member rings are stable
and generally insoluble in the aqueous phase but readily soluble in non polar solvents. An
example of chelating is the reaction of 8- hydroxyquinoline with aluminum ions resulting
in a complex which is soluble in chloroform.
4.2.2 By Ion exchange processes
Ion exchange can either be cationic or anionic depending on the nature of ions being
exchanged
(i) Cation exchange process involves the exchange of metal cations with the
hydrogen ions of the reagent dissolved in the organic phase. Such extractants may
be termed liquid cation exchangers and include organic acids such as alkyl
phosphoric acids and carboxylic acids. The general form of the reactions is shown
by the equation below:
Such reactions are pH dependent and an example is the extraction of zinc using
versatic acid as shown in the reaction;
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2R1R2 CHCOCOOH + Zn2+ = (R1R2CHCOCOO)2Zn + 2H+
Table 4.1 gives typical applications of common liquid cation extractants.
Table 4.1 Liquid Cation Extractants
Anion exchange processes involve exchange of complex metal anions with anions of long
chains alkyl amines. These include all classes of amines from primary to tertiary and
quaternary ammonium types. These extractants are frequently called liquid anions
exchangers. Examples of anion exchange extractants are shown in the table 4.2. An
example is the tertiary amino, tri octyl amine (R3N) which can be used to extract
platinum from acid chloride solution.
R3N + HCl = R3NH.Cl
And
2R3NH.Cl + PtCl62- + (R3NH)2PtCl6 + 2Cl-
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Table 4.2 Hydrometallurgical applications of common anion- exchanging extractants
4.2.3 By solvation with ion association

Solvation involves the replacement of solvating water molecules of an aqua-cation by
organic solvent molecules. Examples of extractants of this type include esters, ethers and
ketones these are shown in table 4.3.
Table 4.3 Common solvating extractants
4.3 Kinetics of Solvent Extraction

Because the metal-extraction separation process involves chemical reactions, rates may
be slow compared with ordinary liquid extraction. Although no single theory can be used
to represent all transfer mechanisms, the two- film theory has proved useful in indicating
the factors that govern rates of extraction.
The critical question regarding metal-extraction (or stripping) kinetics is whether the
chemical reactions that accomplish the phase transfer of the metal are fast or slow relative
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to the prevailing mass transfer rates. Mass transfer rates may be characterized
conveniently in terms of a two-film model, with film mass transfer coefficients being
typically on the order of 10-2 cm/s in liquid-liquid systems. (This value corresponds to an
effective stagnant-film thickness of 10-3cm; a homogeneous reaction zone might lay
within 10-5cm of the interface for a bulk metal concentration 100 times the aqueous
extractant solubility.) Within this context maximum, or mass-transfer-limited, extraction
rates, obtained when the extraction reaction maintains equilibrium at the interface, can be
computed.
4.3.1 The Two-Film Theory
When two immiscible phases, not at equilibrium, are brought into contact, the rate of
transfer of a metal from one phase to the order depends on the extent to which the
concentration of the metal in the two phases differs from the equilibrium values. A
concentration gradient is considered to exist at either side of the interface. It is assumed
that extraction of the metal solute involves transfer from phase B (aqueous) to the organic
phase (S) and if symbol (c) with appropriate subscripts is used to represent
concentrations, then in phase B the rate of mass transfer may be expressed by
(dn/dt) B = kBA(cB cBO)
Where A is the area of the interface
kB is proportionality constant referred to as the film mass transfer coefficient
cB and cBO are the metal concentrations in the bulk of the aqueous phase and at the
interface respectively.
The solute, having passed through the interface or alternatively having undergone
reaction at the interface to produce a new species in phase S, experiences transfer in
phase S away from the interface, the rate is given by:
(dn/dt) S = kSA(cSO cS)
Where kS is the film mass transfer coefficient for phase S.
If steady state situation exists then:
(dn/dt) B = kBA(cB cBO) = (dn/dt) S = kSA(cSO cS)
The film mass transfer coefficient for each phase is a composite term which involves both
the diffusivity of the solute and also the film thickness.
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It is thus evident that agitation favors high extraction rates and this is achieved by:
Decreasing the film thickness on each side of the interface
Increase the interfacial area by creating a more intimate dispersion of the two
phases
Other factors affecting extraction include the phase ratio (which affects the interfacial
area) and the temperature (which modify the diffusivity)
For a simple cation-exchange extraction, such as reaction:
Concentration profiles near the interface are represented by Fig.4.1. The fluxes at the
interface of all four species are related by the reaction stoichiometry. The interfacial
concentrations depend on the bulk-solution concentrations, the interfacial metal flux, and
the respective mass transfer resistances.
Figure 4.1 Concentration profiles near the interface during metal extraction by an acidic
extractant
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A typical solvent extraction flowsheet is shown below:
Figure 4.2 Solvent extraction portion of the Kennecott copper-nickel carbonate process
for deep-sea manganese nodules
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4.4 Process Design and Engineering
Process flowsheet for separation of numerous metals have been published. Synthesis and
design of such processes for a given feed stream require consideration of the following
factors:
1. Choice of Extractant.
For separation of a particular metal, an effective extractant must be chosen that has the
capability of providing high distribution coefficients and high organic-phase loadings.
This choice depends on the chemistry of the metal and the composition of the aqueous
feed solution. For example, a chelating extractant may be appropriate for extracting
copper from a weakly acidic sulfate solution, but an amine may be required for a solution
that has a high level of hydrochloric acid. A practical extractant must also be subject to
regeneration. The extraction must be reversible such that stripping is possible with
minimal consumption of reagents. Stripping should yield a purified and concentrated
form of the metal product. With feed streams that contain several metals, selectivity may
be a major concern. To obtain selectivity one may seek a different extractant for each
metal that is highly specific by virtue of its equilibrium or kinetics properties, or one may
use a single extractant for several metals and design the contacting process to achieve
effective fractionation by exploiting quantitative rather than qualitative differences in
metal chemistry. An example is in the Falconbridge solvent extraction process where
TBP is chosen to extract iron from a chloride feed stream containing copper and cobalt.
Then copper and cobalt chlorides are both extracted into an amine solution. The
separation of cobalt from copper is accomplished by controlling the water-to organic
phase ratios in two separate stripping circuits.
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2. Choice of Diluents, Modifiers, and Extractant Concentration.
The formulation and composition of the organic-phase solution play a major role in
determining both the chemical and physical performance characteristics of an extraction
system. The use of modifiers and mixed extractants alters both equilibrium and kinetics
properties and can have a strong influence on interfacial phenomena. It is particularly
important to formulate a system that minimizes organic solubility in the aqueous phase,
promotes phase disengagement, and prevents emulsion formation. Problems in any of
these areas can quickly render a process uneconomical or infeasible.
3. Choice of Process Configuration. The sequence of processing steps and flowsheet

configuration must be selected concurrently with the choice of extraction chemistry.
Some of the established heuristics of separation process synthesis may be helpful here.
For example, in multimetal fractionation it is probably better to try selective stripping
from a single organic stream than to do multiple selective-extraction operations. The
former approach, if possible, would minimize handling of the total feed stream volume
and presumably reduce solvent losses and reagent consumption.
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Figure 4.1 Solvent extraction of the Falconbridge Nikkelvert A/S matte leach plant for
separation of iron, copper and cobalt
4. Choice of Contacting Equipment

Although each extraction and stripping operation in a metals separation process is
normally operated in a countercurrent mode, either stage wise or in differential contact,
the large distribution coefficients provided by the chemical-reaction basis of the
separations suggest that a large number of stages, or transfer units, are not required. On
the other hand, slow kinetics may restrict efficiency factors considerably so that high
interfacial areas and residence times may be required. These conditions have favored the
use of mixer-settlers. Where kinetics is fast, differential contactors may be preferable
because of smaller power requirements and solvent inventory requirements.
While efficiency is a factor in equipment selection, mechanical considerations often

provide the determining criteria. One must always be sure to minimize solvent losses, and
concern about entrainment and emulsion formation can dictate the mode of operation if
not the choice of contactor. For example, power input for mixing may be limited or the
less viscous phase chosen to be continuous to ensure good phase disengagement.
Task
Devise a case of your own choice, for a process feed stream that can be treated using
solvent extraction then using the design consideration design a suitable solvent extraction
flowsheet to extract the valuable metal from the aqueous phase
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5.0 Electrolytic Processes
Describe the electrolytic processes for metals
Discuss the energy requirements for electrowinning and electrorefining
Discuss the application of solvent extraction and electrowinning in the extraction
of copper from leach solution
Describe the electrorefining of copper and nickel and explain the separation of the
other constituents
Carry out basic energy calculations involving electrolytic cells
5.1 Introduction
Many metals are recovered from solution by cathodic reduction in an electrolytic cell.
This has the advantage of producing the metal as a coherent solid deposit but, if required,
it may often be obtained in the form of a powder by using a high current density.
Theoretically, cathodic reduction of any metal is possible but more reactive metals
require a fused salt electrolyte which is generally at a temperature above that of the
depositing metal. Below is a typical electrowinning cell.
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Figure 5.1 A typical electrowinning cell
5.2 Electrowinning of Metals
Electrowinning is an extraction process in which the cathodic reduction process is used to
recover the sought metal from the electrolyte which is derived from a leaching process.
Generally the anodes used should be inert and support a gaseous evolution reaction;
however soluble anodes can also be used like in the electrowinning of nickel from nickel
matte anodes.
In aqueous electrowinning processes oxygen is evolved, whilst in chloride electrolytes,
chlorine is evolved, and for fused electrolytes the electrolyte and anode composition
determine the anodic reaction.
5.2.1 Electrodes in electrowinning

(a) Anodes
Inert electrodes are preferable because any dissolution at the anode is likely to produce
metal ions which may be reduced cathodically or may form precipitates which
contaminate the depositing metal. For electrowinning of aqueous electrolytes either lead
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based alloys or titanium-based anodes are used, these can be coated with other metals like
platinum to reduce dissolution of the anode. Carbon anodes are exclusively used for
electrowinning of fused electrolytes though recent trends are towards use of inert
electrodes and have involved investigating the use of conducting ceramic materials.
(b) Cathodes
Starting sheets have traditionally been used for electrowinning of aqueous electrolytes,
and these are made from the same metal as that being deposited. These are made from
special separate cells where the metal is deposited on cathode blanks from which the thin
electodeposited sheet can be readily stripped.
5.2.2 Electrolytic cells and electrode configuration in electrowinning
The cells are usually precast reinforced concrete tanks lined with lead or thermoplastic,
generally PVC or HD polythene. Size of cells varies and depends on the number of
electrodes to be accommodated and the inter-electrode spacing. Most cells operate with
cathode groupings in the range of 40 to 50 and in each cell, cathodes are arranged
alternately with anodes. The cathodes are electrically connected in parallel, as are the
anodes and the cells are connected in series the cathodes of one cell being linked with the
anodes of the adjacent cell
5.2.2.1 Energy requirements in electrolytic cells
The reversible decomposition potential, VO, is the nominal potential difference between
anode and cathode that must be exceeded for an overall cell reaction to occur and is given
by (VO =EA EC). The decomposition potential or applied potential (VI) is the potential
that has to be applied to produce a current, I, through the cell. To produce a significant
current through the cell, additional increments of potential are required to overcome the
resistance of the electrolyte and various electrical contacts and the activation over
potentials (the required shift from the equilibrium potential to bring about either
deposition or dissolution).
VI = (EA EC) + A + C + (IR)electrolyte + (IR)contacts
The current efficiency of the cathode is the ratio of the mass of metal actually deposited
to the theoretical mass that could be deposited according to Faradays laws.
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Energy consumption = VIF/ [(A/z) x 3600 x 0.01(CE)]
Where VI is the applied potential in volts, F is the Faraday constant, A the relative atomic
mass and (CE) is the percentage cathode current efficiency. The equation simplifies to:
Energy consumption = 26.8 VI / [(A/z) x 0.01(CE)] kWh.kg-1
5.2.2.2 Electrolyte circulation and agitation

Circulation of the electrolyte serves both to convey the metal ions from the purification
stage and also to provide convective mass transfer within the electrolytic cells. Within an
electrolytic cell anodically generated oxygen substantially increases mass transfer to the
upper part of a cathode producing a higher current density in that area; co-discharge of
hydrogen at the cathode is also known to enhance the mass transfer. Favorable mass
transfer conditions are also provided by air agitation and use of perforated bubble tubes
with small-diameter orifices than use of porous spurgers.
Gas generation at the electrodes and air agitation, particularly if sparging tubes are used,
result in the production of a fine mist of electrolyte to the atmosphere. This is obnoxious
and a health hazard which may be minimized by blanketing the electrolyte surface with a
layer of oil or surface active agent. Thus, ventilation systems to extract acid mist and
improve atmospheric conditions are installed. The figure below shows an example of a
ventilation system:
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Figure 5.2 Cross flow ventilation
Task
Electrowinning and solvent extraction are normally applied in metal extraction; review
the application of the two hydrometallurgical processes in the extraction of copper from
its ores.
5.3 Electrorefining of Metals

In an electrolytic refining process the cathodic reaction is the reverse of the anodic
reaction. The anode consists of impure material and it dissolves as shown:
M = Mz+ + ze
Whist the cathodic reaction is the deposition of the dissolved metal:
Mz+ + ze = M
Thus the reversible potential Vo is zero and VI
VI = A + C + (IR)electrolyte + (IR)contacts
Thus, the applied potential in electrorefing is substantially less than in electrowinning and
the power consumption is significantly reduced.
5.2.1 Electrorefining as a two-stage purification process
In electrowinning (cathodic metal reduction) process the metal with the most positive
potential will deposit preferentially leaving in solution the metals with a more negative
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potential thus effecting separation. In anodic metal dissolution process, the anode
impurities which have potentials more positive than the working anode potential will
remain undissolved as a residue and are known as anode slime. The metals with the more
negative potentials will dissolve anodically with the major metal
Electrolytic refining is thus a two-stage purification process in which ideally the elements
more noble than the metal being refined remain insoluble at the anode, and the elements
less noble dissolve but do not deposit at the cathode, thus the depositing metal is thereby
purified.
5.3.2 Electrorefining of Copper
The electrorefining of copper will be used here to illustrate the concepts of
electrorefining.
5.3.2.1 Preparation of Anodes
Molten blister copper maybe refined directly, in a rotary type furnace or cast blister
copper is remelted in a hearth or shaft furnace together with any available scrap and
anode scrap copper. Air is blown through the molten copper to reduce the sulphur content
until approximately 6% Cu2O is present. Impurities are also oxidized and the oxide dross
is skimmed off. The metal surface is then covered with small coke or coal and poled with
green wood to produce tough pitch copper which contains approximately 0.5% Cu2O
which ensures that a flat surface is produced on the anodes during solidification. In recent
practice poling has been replaced by gaseous reduction using natural gas, propane or
ammonia. The refined copper is then cast into anodes of average dimensions (1 x 0.9 x
0.05m) with a mass of 300 - 400kg uniformity in weight is crucial in order to prevent
excessive anode scrap.
A recent development is the use of the Hazelett casting machine which uses the principle
of continuous water cooled strip casting. This produces anodes which are dimensionally
highly accurate and have half the thickness of cast anodes. This allows for more
electrodes per electrorefining cell hence increase in productivity. However the shorter life
of the anodes means an increase in anode scrap due to more frequent replacement.
Composition of the anodes varies from plant to plant but the copper content is usually
99.4 99.8% with a range of impurities present in small amounts.
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5.3.2.2 Electrolytic plant and operation
The general flow sheet for the electrorefining of copper is given by figure 5.3. The
electrolytic cells are made of cast reinforced concrete lined with 6% antimonial lead or
PVC sheet. The anodes alternate with the cathode starting sheets, with each set of
electrodes electrically connected in parallel and the cells in series as in electrowinning.
Blister copper & Scrap
Anode
furnace Anode srap
Anode Scrap
Starting
Sheet cell Anodes
Starting
sheets Electrorefining
cells Electrolyte Cathode
Electrowinning
bleed copper
Anode slimes Impure

Electrowinning
copper
Soln
Acid boil
Crude
Evaporation
NiSO4
Residue
Concentrated acid
Cupellation Cathode
copper
Silver bullion
Figure 5.3 Electrorefining of copper-general flowsheet
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5.3.2.3 Anode impurities-electrolyte and slimes treatment
The anode impurities include; sulphur, selenium, lead, gold, silver, and platinum metals
remain insoluble during electrolysis and are found almost entirely in the anode slimes.
Sulphur, selenium and tellurium are present as compounds such as Cu2S, Cu2Se and
Cu2Te in the original anode and stay unchanged whilst lead forms the insoluble PbSO4 by
reaction with the electrolyte. Bi, Fe, Ni and Co dissolve completely with copper but
arsenic and antimony dissolves partially and contaminates both the electrolyte and the
anode slime. To avoid co-deposition of the soluble impurities, a bleed is taken from the
electrolyte and purified and then fed back to the circulating electrolyte at a rate sufficient
to maintain the impurity levels in the cathode copper within specific limits.
(a) Treatment of the bleed stream
The purification treatment consists of two consecutive processes:
Electrodeposition using inert electrodes
Evaporation and crystallization of Ni(II) and iron sulphate and other metal
compounds from solution
Solvent extraction
The electrodeposition process depends on the impurities present; it can have either two or
three stages:
Electrowinning using copper starting sheets and producing commercially pure
copper cathodes
The second and third stages produce impure copper that requires refining in the
anode furnace and treatment in a smelter respectively.
The evaporation process brings about crystallization of impure nickel sulphate
contaminated with other metal sulphates (CuSO4, FeSO4, Fe2(SO4), Co(SO) 4 and other
compounds. The crystals are separated and the residual concentrated acid which is fed
back into the circulating electrolyte to maintain the acidity. The nickel sulphate is
purified and the cobalt also recovered.
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(b) Treatment of anode slimes
The slimes are treated with hot sulphuric acid to dissolve out copper and other
compounds. The residue, now a concentrate of precious metals is filtered or centrifuged,
washed free of solution, and dried. It is fed to a cupellation furnace from which silver
bullion is obtained which is cast into anodes for electrolytic refining of silver.
Task
Using the format we have used for the electrorefining of copper, review the
electrorefining of nickel
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6.0 Hydrometallurgical extraction of gold: A Case Study
At the end of this section you should be able:
Discuss the mineralogy of gold ores and explain how it contribute to extraction
Develop a processing flowsheet based on mineralogical findings
Explain the theories of cyanidation
Appraise alternative lixiviants for gold leaching
Compare and contrast the various gold recovery techniques
Discuss techniques of effluent treatment
6.1 Ore Mineralogy and Geochemistry of Gold

Gold has two main oxidation states i.e. +1 (aurous) and +3 (auric). McQuiston and
Shoemaker(1975) proposed a classification of gold ores based on extraction and
Boyle(1979) distinguished ten types gold deposits.
6.1.1 Classification of gold ores based on extraction
(a) Native gold ores
The gold is removed by gravity separation, amalgamation and/or cyanidation
(b) Gold associated with sulphides
Occurring either as free particles or disseminated in sulphides. Auriferous pyrite with
gold finely disseminated in its matrix is rather common (pyrite is relatively stable in
cyanide, but pyrrhotite, if present, dissolves and increases the cyanide consumption)
(c) Gold tellurides
Usually occur along with native gold and sulphides. Calaverite and krennerite are
minerals containing about 40% gold, and sylvanerite contains about 25% gold (in
addition to 13% silver)
(d) Gold in other minerals
These include arsenic and/ or antimony (e.g. aurostibnite,AuSb2), with copper
porphyries(as selenide and telluride), with lead and zinc minerals, and with carbonaceous
materials.
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6.1.2 Auriferous Deposits
1. Auriferous porphyry dykes, sills, stocks; auriferous pegmatites; coarse-grained
granitic bodies; aplites and albitites
The gold content of these granitic rocks is low in the order of 3ppb. Certain albitites,
quartz-feldspar porphyry dykes, and rocks with indigeneous pyrite and/or pyrrhotite may
contain up to 0.1ppm gold
2. Carbonatites and carbonatite-related bodies
Generally low gold around 0.005ppm and the sulphide phase is the one which normally
contains the gold. Very few carbonatitese are enriched enough for economic recovery.
3. Auriferous skam-type deposits
These contain early developed Cu-Fe-Mg silicate and oxide minerals, along with
carbonate, sulphide, and arsenide minerals. Gold is contained as native or in the form of
tellurides and is associated with Fe, S, Cu, Ag, Zn, Pb, Mo, As, Bi, Te and trace tungsten.
4. Gold-silver and silver-gold veins, mineralized pipes, and irregular silicified
bodies in fractions, faults and zones
Composed of quartz, carbonate minerals, pyrite, arsenopyrite, base-metalsulphide, and
sulfosalt minerals. Principal gold minerals are native gold and gold tellurides and in some
deposits aurostibnite, the other associated minerals being Cu, Ag, Mg, Ca, Zn, Cd, B, Si,
Pb, As, Sb, S, W, Mn, and Fe
5. Auriferous veins, lodes, sheeted zones, and saddle reefs in fault and fracture
Principle minerals are native gold, auriferous pyrite, and auriferous arsenopyrite
associated with pyrite and arsenopyrite, and galena, sphalerite, chalcopyrite, and
pyrrhotite may also occur.
6. Gold- silver and silver-gold veins, lodes, stockworks and silicified zones in a
complex geological environment with sedimentary, volcanic, and various igneous
intrusive and granitised rocks
These ore bodies are mainly quartz veins, lodes, and silicified and carbonated zones.
Gold is mainly free gold and may also be present as tellurides and disseminate in pyrite
and arsenopyrite.
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7. Disseminate and stockwork gold-silver deposits in igneous, volcanic and
sedimentary rocks.
There are generally three subgroups:
Disseminated and stockwork gold-silver deposits in igneous strata
Disseminated gold-silver and silver-gold occurrences in volcanic flows
Disseminated gold-silver deposits in volcaniclastic and sedimentary beds
Most deposits are characterized by introductions of Ag, Au, Hg, Ti, B, As, Sb, Se,
Te, and base metals. The gold if disseminated in finely divided form (<5)
8. Gold deposits in quartz-pebble conglomerates and quartzites
Constitute the largest and most productive gold mines. These are marked by presence of
abundant pyrite and/or hematite along with trace amounts of sulphides, arsenides, and
uranium minerals. Gold is in the form of very fine native gold (<80) in the
conglomerates or quartzites and associated with Fe, S, As, Au, Ag, Cu, Zn, Pb, Ni, Co
and PGMs (platinum group metals)
9. Elluvial and alluvial placers
These produce gold nuggets and dust with low silver content. Heavy minerals like
monazite, scheelite, and cinnabar, as well as pgms may accompany elluvial and alluvial
gold.
10. Miscellaneous sources of gold
These include chalcopyrite, copper-nickel sulphides, pyrite, arsenopyrite, other base-
metal sulfides, selenides, arsenides, and sulfosalts. Gold follows the base metal during
smelting and is recovered from the slimes during electrorefining of the base metals.
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The following tables show the mineralogy of two types of ores being processed locally:
Table 8.1 The Redwing Mine ore

Mineral Abundance
Pyrite 65.0
Pyrrhotite 20.0
Galena 8.0
Chalcopyrite 5.0
Gold <0.5
Table 8.2 The How Mine ore

Mineral Abundance
Pyrite 45.0
sulphide 24.0
Pyrrhotite 18.0
Galena 8.0
Chalcopyrite 5.0
Gold <0.007
Task
Analyse the two ores and appraise the problems that can be faced when extracting gold
from these ores due to the composition of the ores? How have the respective mines
countered the challenges? What are the alternative processing routes for extracting the
gold? How would classify the ores according to the classes already covered
6.3 The Cyanidation Process
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The cyanidation process was invented by MacArthur and the Forrest brothers in 1887,
and has become the basis of hydrometallurgical extraction of gold. Several theories have
been proposed to explain the cyanidation process, which include: The oxygen theory
(which states that oxygen is vital to the dissolution of gold), The hydrogen
theory(suggests that hydrogen is involved in the process), hydrogen peroxide
theory(suggests that hydrogen peroxide is formed as an intermediate product), cyanogen
formation( suggests that oxygen is required for the formation of cyanogens gas which
then acts as an active reagent in the dissolution), Corrosion theory( suggests that
cyanidation is similar to a metal-corrosion process in which oxygen dissolved in solution
is reduced to hydrogen peroxide and hydroxyl ion).
Task
Write all the equations associated with the cyanidation theories, how does each assist in
explaining the cyanidation process?
6.3.1 The Mechanism of Cyanidation

Cyanidation is a heterogeneous process which can be summaries by the following steps:
Absorption of oxygen in solution
Transport of dissolved cyanide and oxygen to the solid-liquid interface
Adsorption of the reactants (CN- and O2-) on the solid surface
Electrochemical reaction
Desorption of the soluble gold-cyanide complexes and other reaction products
from the solid surface
Transport of the desorbed products into the bulk solution
6.3.2 The effect of oxygen on cyanidation
Adequate aeration is generally adequate to give good results in cyanidation although
oxidizing agents such as sodium peroxide, potassium permanganate, bromine, and
chlorine, have been used. It is the dissolved oxygen that is crucial in cyanidation and it
depends on the following parameters:
The altitude(barometric pressure)
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The temperature of the solution
The type and intensity of agitation
The ionic strength of the solution
At low cyanide concentration, the oxygen pressure has no effect on the gold dissolution
however at high cyanide concentration, where the rate of dissolution is independent of the
solvent concentration, the reaction is dependent on oxygen pressure.
6.3.2 The effect of cyanide concentration
At atmospheric pressure, the cyanidation process is not dependent on cyanide
concentration. At room temperature and atmospheric pressure, 8.2mg/l of oxygen are
dissolved in water, equivalent to 0.26x 10-3. Hence, the required sodium cyanide (Mr 49)
concentration should be at least 0.051g/l (49 x 4 x 0.26x 10-3). Higher than 0.051g/l
sodium cyanide concentration cannot affect the rate of gold dissolution, since at the
atmospheric pressure it is controlled by the constant oxygen concentration in solution.
6.3.3 Other factors affecting cyanidation
Other factors affecting cyanidation are:
pH and Eh
alkali additions
foreign ions
flotation reagent
side reactions
particle size
temperature
Task
Explain how each factor contributes to the cyanidation process. What are the optimum
values for an ore of your choice?
6.4.1 Chemical enhancement of cyanidation

The presence of small amounts of Pb, Hg, Bi, and Th salts accelerates the dissolution of
gold. Considering the electrode potentials of these ions in cyanide solutions, proves that
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gold displaces the ions of these four metals. The rapid dissolution of gold in the presence
of these ions might be due to an alteration of its surface characteristics caused by alloying
with the displaced metals. Lead nitrate is a common additive to the cyanidation process
and is referred to as Leach aid.
The rate of dissolution of gold can also be enhanced by the addition of some peroxygen
compounds these is because hydrogen peroxide is an intermediate product in gold
dissolution in alkaline cyanide solutions. However the concentration of the peroxygen
compounds must be carefully controlled to minimize cyanide consumption.
6.4.2 Physical enhancement of cyanidation
There a number of physical ways used to enhance the cyanidation process, which
includes:
ultrasonic treatment of pulp
mixing efficiency
pressure cyanidation
intensive cyanidation
6.4.2.1 Ultrasonic treatment of pulp
This is used to produce further breakage, it causes a widening of secondary fissures in the
ore, and allows exposure of new surface that include microscopic gold particles. Contact
of the new surfaces with leaching reagents enhances both the rate of extraction and the
degree of extraction.
6.4.2.2 Mixing efficiency
Dissolution of gold is also enhanced by improving agitator and pachuca mixing
efficiency and control, as well as the availability of techniques to measure the efficiency
of continuous leaching devices. Common problems encountered with pachucas are
sanding up (thus reducing the residence time) and inefficient mixing.
A row of leaching vessels arranged for continuous leaching of pulp is subject to short-
circuiting, whereby an ore particle finds its way through the system with a shorter
residence time than designed. The use of large leaching vessels in batch mode (rather
than continuous) is preferable.
6.4.2.3 Pressure Cyanidation
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A combination of high temperature and pressure has been used to achieve high recoveries
of gold from complex ores containing sulphides, tellurium, selenium, arsenic, antimony,
and bismuth, this has shown low consumption of oxygen indicating limited oxidation of
sulphides and other contaminants. This method yields both high recoveries for refractory
ores and also increases the rate of extraction.
6.4.2.4 Intensive Cyanidation

Applied to gravity concentration concentrates. In the past amalgamation has been used to
upgrade these concentrate (there are still a number of local plants using amalgamation for
upgrading the concentrates however its major application is in small scale mills) but has
recently been replaced by intensive leaching because of environmental and security
concerns in large scale plants.
Oxygen partial pressure in solution is the most critical factor determining the cyanidation
rate, thus the use of pure oxygen. Increased dissolved oxygen content allows the use of a
higher NaCN solution than in normal leaching. Vigorous agitation of the pulp accelerates
the mass transfer between liquid and solids. Operating temperature is between 30 -35oC.
There are a number of intensive leach reactors and details of local applications are given
below.
6.4.2.4.1 The operation of Inline Leach Reactor (ILR) at a local mine
The (ILR) is basically an intensive leaching process reactor which is used to treat
concentrates from the gravity concentration section. It is designed to treat coarse gravity
gold concentrate produced by gravity concentration and recover the solid gold into
solution. The ILR uses the concepts of the laboratory bottle roll tests. It consist of a
1.7 x 1, 8 m horizontal drum that rotates at a speed of 1.5 rpm at a power of 5.5KW.
Process description
Concentrates from the Knelson Concentrator (KC) are collected into the feed cone where
it is decanted to remove excess water prior to injection into the drum. At the start of the
leaching cycle, feed from the storage hopper is drained into the reactor drum, water and
the leaching reagents (sodium cyanide, sodium hydroxide and hydrogen peroxide) are
prepared in their respective tanks and are added to the solution storage tank to form the
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leach solution of 2-3%cyanide strength, 20ppm dissolved oxygen and a pH of 11.5 -12.5.
lixiviant (leaching solution) flows from the solution storage tank into the rotating reactor
drum and contacts the solids. The lixiviant is recirculated continually at a flow rate of 2
tons/hour to ensure fresh solution is in contact with the solids. The loaded lixiviant
overflows the reactor drum to the pregnant solution sump and is pumped to the solution
storage tank.
The residence time i.e. the leach cycle is usually six hours after which the reactor drum is
stopped and the solution is drained into the solution storage tank for clarification. The
reactor drum is then rotated adding water to wash the remaining solution and the process
is repeated until the gold assays are less than 10ppm. The wash solution is mixed with the
leach solution in the solution storage tanks and allowed to settle before the clarified
solution is pumped to the electrowinning circuit for gold recovery. The barren solution is
returned from the eluant tank to the ILR circuit to maximize the usage of residual
reagents especially residual cyanide.
The barren solids are drained out by adding water and reversing the drum rotation and
they are pumped to the milling circuit for further liberation of the value.
Concentrate from Reagent addition

Knelson concentrator
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Concentrate hopper
Solids
Pregnant Disposal
solution hopper
Excess
water
Electro
wining
Reactor
Drum
Water
addition
Solution
Sump
Figure 6.1 Inline intensive leach rector circuit at a local mine
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Process parameters
(a) Cyanide concentration
Since this is an intensive cyanidation process the concentration of cyanide is essential. A
2-3% CN concentration is optimum for the operation of the ILR and this is achieved by
dissolving 600kg of NaCN in 1.58m3 of water.
(b) pH
The pH is regulated within 12-13 ranges to prevent excessive loss of cyanide by
hydrolysis this is attained by dissolving 150 Kg of NaOH in 1.58m3 of water.
(c) Oxygen concentration
20- 30ppm dissolved oxygen is used and this is attained by mixing 50% hydrogen
peroxide solution with water.
(d) Gold concentration
Assays of the solution are taken hourly to check whether dissolution is taking place.
Assays range between 100 -1000ppm.
6.4.2.4.2 Operation of the Acacia Plant at a local mine
Concentrates from a high intensity Concentrator are charged into the acacia reactor and
then water is injected into the reactor in order to remove fines. The fines overflow on a
launder and are then discharged as tailings into a sump box. Desliming of concentrates
is done because slimes are hard to treat and form a prohibitive layer on gold bearing
particles thereby limiting gold dissolution.
The lixiviant consist of 40kg sodium cyanide flakes, 3kg leach aid and 15 kg of a caustic
soda which are added into the leach tank where they are thoroughly mixed for about 30
minutes, and the solution is allowed to circulate in and out of leach tank for about 22
hours for maximum gold dissolution to take place. The pregnant solution is then
transferred into an electrowinning cell which has cathodes made of wire wool and steel
anodes.
6.4.2.5 Cyanide Regeneration
During cyanidation base metal compounds also dissolve giving rise to complex
cyanogens compounds which will remain in solution. If the concentration of these
cyanogens compounds is high the cyanide solution will become inefficient as lixiviant for
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gold. The general method for cyanide regeneration is by acidification of its solutions with
sulfuric acid, SO2 or CO2. The acidified solution is transferred to a closed tank in which it
is stripped by aeration. The acidification step produces colloidal precipitates of base
metal-cyanide complexes which are very difficult to remove and tends to interfere with
the stripping caustic absorption operations. There are basically two methods used to
separate cyanide from the colloids:
Filtration
Ion exchange resin
6.5 Alternative Leaching Reagents for Gold
Sodium cyanide is the predominant lixiviant for gold ores and it yields excellent
recoveries in a variety of ores. However it has its own disadvantages which include:
It is poisonous
Not selective i.e. it forms complexes compounds with a variety of metal ions
Relatively slow
Some of the cyanicides are:
(a) Base metals
Fe, Cu, Ni, Zn; these form complex cyanides
(b) Sulphides
Pyrrhotite, zinc blende (ZnS), CuS and Cu2S; these form thiocynate with cyanide
(c) Arsenides and antiminides
FeAsS, Sb2S2, Cu3SbS3, Cu3AsS3, Ag3SbS3; these form either thiocyanate, cyanate, or
complex cyanides
Alternative lixiviants for gold leaching include:
Thiourea
Thiosulphate
Halogens and halides
Sulfocyanides
Ferrocyanides
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Task
Despite the disadvantages of sodium cyanide as a lixiviant in gold leaching, it is still the
main lixiviant; Comment on its application in cyanidation. Write up the mechanisms of
the leaching of gold using thiourea and thiosulphates, what are the advantages of these
reagents? Why are they not being widely applied in gold extraction.
6.6 Recovery of gold from solutions

Gold can be recovered from pregnant solutions by one or a combination of these
processes:
Zinc cementation
Activated carbon adsorption
Ion-exchange/solvent extraction
Electrowinning
6.6.1 Zinc Cementation

Cementation a heterogeneous redox system in which aurocyanide and cyanide ions have
to transfer to the zinc surface, the reactants have to be adsorbed on the zinc surface, the
reduction reaction occurs on the zinc surface, the products of the reaction are desorbed
and are transported to the bulk of the solution. The reaction is based on the
electrochemical series, where a more reactive metal will displace less reactive metal ions.
When cyanidation was commercialized in 1890, zinc shavings were used to precipitate
gold from solution. Addition of lead salts resulting in the formation of a Zn-Pb alloy on
the zinc particles inhibits passivation of zinc surfaces is beneficial to the cementation
process. The use of zinc dust immensely increased the yield by increasing the surface
area.
2Au(CN)2- + Zn 2Au + 2Zn(CN)42-
2Au(CN) 2- + Zn + 3OH- 2Au + HZnO2- + 4CN- + H2O
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Zinc can also react in alkaline cyanide solutions to produce hydrogen
Zn + 4CN- + 2H2O Zn(CN) 42- + 2OH- + H2
Zn + 2H2O HZnO2- + H+ + H2
Thus it is possible that precipitation of some gold may not proceed directly but through
the intermediate formation of hydrogen.
Au(CN) 2- + H2 Au + 2H+ + 2CN-
It is known, nevertheless, that gold is not precipitated from cyanide solutions by
hydrogen at atmospheric pressure, at higher pressure and temperature, the reduction of
aurous ions by hydrogen takes place at a relatively slow rate.
The overall reaction for zinc cementation is given by:
Zn + Au(CN)2- + H2O + 2CN- Au + Zn(CN) 42- + 3OH- + 0.5 H2
The rate of the reaction was found to be controlled by the transfer of the Au(CN)2- ions.
The presence of oxygen in solution decelerates the reduction reaction and also increases
the consumption of zinc dust, thus the invention by T.B. Crowe of the vacuum tower to
remove air and dissolved oxygen from the pregnant solution was a welcome
development.
6.6.1.1 Efficient cementation practice
The requirements for the efficient cementation of gold from cyanide solution with the
addition of zinc powder are as follows:
(i) the pregnant solution should:
be clarified to less than 5ppm solids
be deaerated to about 1ppm oxygen
have a free cyanide concentration higher than 0.035M
have a pH in the range of 9 to 11(with adequate lime addition)
contain an adequate proportion of lead nitrate(about 0.5 to1 part of lead
nitrate to 1part of gold) and not a high concentration of lead
(ii) Adequate addition of high purity zinc dust (5 to 12) parts of zinc per part of
gold)
Task
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Give a detailed account of the Merrill-Crowe precipitation process explaining each
step fully.
6.6.2 Activated Carbon Adsorption

After the development of a process of stripping gold from carbon by Zadra (1950) carbon
adsorption processes had a great breakthrough but it took time for the industry to adopt it
in favor of cementation process. Activated carbon is not homogenous and the softer the
carbon the higher the activity, thus the soft carbon lost due to attrition is the most active
portion. When selecting carbon, the resistance to attrition should be evaluated and the
carbon with the highest activity after attrition should be selected.
The mechanism of the adsorption process is not well understood, however these theories
are thought to apply:
The Au(CN)2- ion is adsorbed as such and held by electrostatic or Van der Waals
forces
The gold compound is altered to some other form during the adsorption process
Metallic gold is precipitated on the carbon
The adsorption process consists of three distinct operations:
Loading: adsorption of gold from solution onto the carbon
Elution or stripping :desorption of gold from carbon
Metallic gold production: electrowinning or cementation of gold from
concentrated solution
6.6.2.3 Loading of carbon
Fundamentally there are three main carbon adsorption techniques:
Carbon in pulp (CIP): activated carbon is directly mixed with the leached gold-ore
pulp
Carbon-in-leach(CIL): the activated carbon is added to the ore pulp in the mixing
tanks as cyanidation takes place
Carbon in columns/solution (CIS): clarified or semi clarified gold solutions percolate
through columns packed with activated granular carbon.
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Carbon with high abrasion resistance is preferred for CIL and CIP processes in order to
prevent loss of gold in fine carbon. Most of the contaminants contained in gold ores are
partially soluble in cyanide and are adsorbed on the carbon along with gold. Gold will
load in preference to copper. Mercury will follow the gold and must be retorted from the
final product. Pb, Zn, Co, Ni, As, and Sb will also be adsorbed, but usually they are at
very low concentrations and do not cause much problems
6.6.2.3.1 Factors affecting gold adsorption

(a) The ionic strength of the gold solution plays a significant role in the adsorption
mechanism. Calcium aurocyanide appears to be the most strongly adsorbed complex in
the following order:
Ca2+> Mg22++ > H++> Li+ > Na+ > K+
(b) Cyanide concentration
High free cyanide concentration is detrimental to adsorption but it is also known to
subdue co-adsorption of copper, thus a compromise on free cyanide concentration is
recommended for copper containing gold ores.
(d) pH
Since both hydrogen and hydroxide ions tend to adsorb to carbon, the pH affects the
adsorption capacity of carbon. The equilibrium gold loading increases with lower pH.
Where pH is adjusted with lime, high calcium concentrations will enhance gold
adsorption while high pH will decrease it.
(e) Particle size
The smaller the particle size of carbon, the higher the surface area and hence gold
adsorption is enhanced.
6.6.2.4 Elution or Stripping
Activated carbon, being an excellent adsorbent of gold it does not relinquish the gold
easily, stripping is thus carried out to separate gold from the carbon and a number of
stripping techniques are applied. Chemical treatment may be required before or after the
elution, may be required to remove slimes from the pores of carbon. Calcium carbonate
and/or sulphate often precipitate in the pores of carbon during loading. It so known as
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acid washing and it involves the use of hot dilute acid (3% HCl) at approximately 90oC is
used to remove calcium and silica from the carbon and hence enhance the elution
kinetics. It may also help to remove some of the base metals such as zinc, copper and
nickel from the loaded carbon. A thorough water-wash is necessary before acid leaching
and after in order to remove the HCN formed during the acid washing process. A caustic
neutralizing wash is also required before carbon is recycled. The stripping techniques are
as follows:
(a) The atmospheric Zadra process.
Gold is eluted from loaded carbon with a solution containing 0.1 -0.2% NaCN and 1%
NaOH heated at 85-95 oC and at atmospheric pressure. Precious metals are stripped by
percolating the hot solution through the loaded carbon bed. Gold and silver are then
electrowon from the solution. The barren solution is then reheated and recycled through
the carbon. The process requires 24 to 60 hours, suitable for small-scale operations
because of a low capital cost and operating costs but the long cycle times make it
unsuitable for large-scale gold mines.
(b) The alcohol stripping process
An extension of the Zadra process it adds 20% volume alcohol to the stripping solution
this has an effect of reducing the cycle time to five or six hours, thus the size of the
stripping section is drastically reduced. The eluant composition is thus, (0.1 NaCN, 1%
NaOH, and 20% ethanol at 80 oC) carbon stripped by this method does not require
frequent regeneration, though the process is prone to fire hazards because of the use of
alcohol.
(c) High pressure stripping process
Uses high pressure and high temperature to reduce the cycle time to between two and six
hours. The eluant used consists of 0.1% NaCN and 1% NaOH at 160 oC and 350kPa
(50psi). Use of high pressure reduces reagent consumption, carbon inventory, and the size
of the stripping section. Requires high capital for installation
(d) The Anglo-American stripping process
Involves preconditioning the loaded carbon with half a bed volume of 5% NaOH and
1%NaCN for 30minutes to 1hour and then stripping the carbon with five bed volumes of
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hot (110oC) water at a flowrate of 3 bed volumes per hour. The high operating
temperature imposes an operating pressure of 50-100kPa. The total cycle time is 9hours.
High capital costs on installation.
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(e) The Micron gold desorption process
Involves conditioning the carbons in a strong, alkaline cyanide solution followed by
desorption in fractionating column, using the carbon as the column packing and methanol
as the desorbing agent.
Advantages:
Desorption, methanol recovery and reactivation is carried out in a single column
Produces very high grade gold solutions which give high current efficiencies in
electrowinning. These high gold concentrations allow almost complete separation
of gold and silver from copper in the electrolytic cell.
The treated carbon is automatically reactivated to 60-80% of the new carbon.
6.6.2.5 Carbon Regeneration
This is carried out periodically after elution in order to;
Remove organic matter and
Inorganic impurities
That is picked up by the carbon during adsorption and is not removed by elution and
acid washing. It involves heating the wet carbon to 650- 750oC in the absence of air
for up to 30minutes and then either quenching the carbon in water or air cooling in
the cooling section of the kiln or in a hopper(which result in a higher activity).
Traditionally a rotary kiln heated externally is used for the application, but recent
technologies involve;
The vertical regeneration kiln(which can reach temperatures of up to 1090 oC)
The MINTEK regeneration process.(which is capable of reactivating heavily
contaminated industrial carbon)
Task
Carbon reactivation is a crucial step in gold processing, with reference to the Mintek
process, explain how reactivation of carbon is attained
6.6.2.6 Electrowinning of gold from cyanide solutions
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Electrowinning is the standard procedure for plants employing CIL or CIP. The gold
laden cathodes are washed, dried, and smelted, or treated with acid to remove the excess
of iron and then smelted. Recovery of gold by electrowinning from the pregnant eluant is
faced with a challenge of low current density (current density is proportional to the gold
content of the electrolyte). Because of the low gold content of the strip solutions (range
from 0.035 to 0.9g/l) the current efficiency during electrowinning will be very low. A
number of electrolytic cells have been developed to counter the challenge of low current
efficiency and these include:
(a) The Zadra electrowinning cell
Uses a boxlike frame cathode filled with steel wool this increases the surface area of the
cathode and hence assist in obtaining the permissible current densities even at low gold
concentration of the pregnant solution. To provide the necessary deposition area, a long
electrolytic cell to accommodate enough cathodes.
(b) The Anglo-American Research Laboratories (AARL) cell
A further development of the Zadra cell modified the Zadra cell by using a cation-
permeable membrane to divide to anode cathode compartments with different anolytes
and catholyte circulations. The pregnant electrolyte flows through the cathode basket,
whereas a strong alkaline solution circulates through the anode compartment.
(c) Mintek steel wool Cell
It is a rectangular cell with pervious cathodes packed with steel wool and stainless steel
perforated anodes (or stainless steel mesh anodes to ensure uniform flow of solution
through the cell). The electrodes are sized to fit down and along the bottom of the
rectangular tank so that the electrolyte has to flow through the electrodes during its
continuous circulation.0.5kg of steel wool can take up to 2kg gold before the cathode
becomes blocked by gold deposit. N.B. It uses parallel solution and current flow and thus
has more uniform packing in the cathodes and hence a more uniform flow of the pregnant
solution than the cylindrical Zadra cells. The loaded cathodes are calcined at 700 oC for
20 hours and the calcine is mixed with 40%borax, 30%sodium carbonate and 25% silica
and is melted at 1300 oC.
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Task
We have so far looked at the use of zinc cementation and carbon adsorption as methods
of recovering gold from pregnant solution. Review the use of IER and SX in the
extraction of gold.
6.7 Destruction of cyanide in gold-mill effluents

Cyanide/water recovery from tail slurries may be required in areas where water is scarce
or where water is abundant due to high rainfall. Water should be recycled to the mill and
any excess water should be disposed of after rigorous treatment, for removal of cyanide
and other metal contaminants. Cyanide should be considered a transient pollutant since its
toxic properties decrease rapidly over time without the need of destroying it with
chemical agents. Natural degradation of cyanide is caused by:
Volatilisation
Photodecomposition
Biodecomposition and
Conversion to thiocyanite
Despite the natural degradation of cyanide, sometimes it has to be destroyed in order
preserve the environment and to comply with environmental regulations. The following
processes lead to quick and efficient destruction of cyanides:
Alkaline chlorination
INCOs sulphur dioxide-air process
DEGUSSAs hydrogen peroxide process
Biological treatment
(a) The alkaline chlorination process
Oxidizes free cyanide-metal complexes in tailings pond water to carbon dioxide and
nitrogen gas, and cause the precipitation of heavy metals as hydroxides.
CN- + Cl2 CNCl + Cl-
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CNCl + 2OH- CNO-Cl- + H2O
2CNO- + 3Cl2 + 6OH- 2HCO- + N2 + 6Cl- + 2H2O
The destruction of free cyanide (NaCN), thiocyanate (SCN-), and copper cyanides is
achieved by oxidation, as depicted in the following reactions;
2NaCN + 6NaOH + 4Cl2 + 0.5O2 8NaOH + 2CO2 + 3H2O +N2
2Na2Cu(CN)3 + 28NaOH + 16Cl2 2Cu(OH)2 + 6CO2 + 32NaCl + 12H2O + 3N2
NaSCN + 4NaOCl + 2NaOH NaCNO Na2SO4 + 4NaCl + H2O
(b) INCOs SO2 process for cyanide removal

Is based on the oxidation of cyanide (free or complexed with transition metals other than
iron and cobalt)
CN- + SO2 + O2 +H2O CNO- + H2SO4
Copper ions catalyse the reaction and when the copper concentration in the tailings is
insufficient some copper sulphate has to be added. The optimum pH is between 8 and 10,
temperature has no significant contribution in the range of 5 to 60oC. Concentration of
SO2 in air is at or below 2%, dilute roaster gases of sulfite solution be used. In the
presence of sufficient copper catalyst the rate controlling step in the oxidation of cyanide
is the transfer of oxygen into solution, thus well agitated reactors are preferred.
(c) Detoxification of cyanide effluents with hydrogen peroxide
Hydrogen peroxide oxidizes cyanide without the formation of toxic intermediates.
Oxidation of cyanide
CN- + H2O2 CNO- + H2O
Hydrolysis of CNO-
CNO-+ 2H+ + H2O CO2 + NH4+, OR
CNO- + OH- + H2O CO32- + NH3
Depending on pH.
If excess hydrogen peroxide is left in the treated water, it rapidly decomposes,
H2O2 H2O + O2
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7.0 Aluminum Extraction Processes- A Case Study
At the end of the section you are expected to:
Describe the bayer process with the aid of a flowsheet
Appraise how the mineralogy of the ore affects purification of bauxite
Explain the mechanisms of the processes involved
Describe the Hall-Heroult process
Appraise any alternative electrowinning process for aluminum extraction
7.1 The Bayer Process

Aluminum is almost exclusively extracted from purified alumina by the Hall-Heroult
electrowinning process. The alumina must be of high purity and it is produced by
purification of bauxite using the Bayer Process. Bauxite ore types are important since the
difficulty of digestion depends on the form of the hydrated aluminum oxide present.
Aluminum in bauxite usually exists in one of three forms:
With silica and oxide of iron as the major impurities. Bauxite ores high in gibbsite are
less costly to treat because of the relative ease of dissolution of gibbsite. Bauxites
containing the monohydrated minerals in large quantity are more difficult to leach,
require higher temperatures and pressure for complete digestion, and are more costly to
treat. Consequently, bauxites may be classified as low cost or high cost. Although the
majority of the bauxite processed is low cost (high gibbsite), this type is estimated to
constitute only 12% of total bauxite reserves.
The cost of capital equipment for a Bayer processing plant is related to the amount of
monohydrated alumina present (boehmite or diaspore) and to the amount of iron oxide
present. The first relates to the refractory nature of ore and the second to the amount of
material that must be handled and separated. Hill and Robson have estimated capital cost
ratios for Bayer plants treating various types of bauxite ore. Capital costs of a bauxite
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containing 50% of the alumina as the monohydrate are estimated to be 40% higher than
for typical low-cost bauxite.
The Bayer process involves the dissolution of aluminum minerals in aqueous hydroxide
and it can be represented by the following steps:
1. Nonoxidative dissolution of hydrated aluminum minerals.
2. Solid-liquid separation to remove ferric oxide, silica, and silicates.
3. Cooling, seeding, and precipitation of gibbsite, Al(OH)3.
4. Calcining of gibbsite to produce pure Al2O3.
The chemical reactions involved in dissolution are:
Ores containing essentially pure gibbsite may be digested at temperatures of 1500C while
boehmitic ores require temperatures in the range of 230-25O0C. These temperatures
reflect the differences in the solubilities of the various hydrated aluminum minerals. The
flowsheet for the bayer process is shown in figure 9.1.
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Figure 7.1 Bayer process for recovery of high purity alumina from bauxite
Task
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Considering the processing steps in the bayer process, suggest the mechanisms of the
process and write short notes on the kinetics of the process.
7.2 The Hall-Heroult Process
This is fundamentally an electrowinning process of aluminum from a fused electrolyte.
The fused electrolyte consists of:
Cryolite
Sodium hexafluouraluminate(III) (Na3AlF6)
8% Calcium(II) fluoride ( to lower the Specific gravity and improve electrical
conductivity)
Extra aluminum (III) fluoride in excess of cryolite composition (to improve the
current efficiency)
Alumina content is maintained above 2% to prevent discharge of fluoride ions at the
anode which would cause a non conducting film to develop over the anode which would
result in an increase in resistance and hence a rapid rise in voltage called the anode effect.
7.2.1 Reaction Mechanism
(i) The first step is ionization of cryolite ions on melting by the reaction:
Na3AlF6 = 3Na+ + AlF63-
(ii) Then the dissolution of alumina in cryolite
Al2O3 + 4AlF63- = 3Al2OF62- + 6F-
The cathodic reaction involves direct reduction of the anionic species:

AlF63- + 3e = Al + 6F-
AlF4- + 3e = Al + 4F-
The anodic reaction involves the oxidation of carbon to carbon dioxide:
2 AlF63- + 2Al2OF62- + C = 6 AlF4- + CO2 + 4e
However the anode products contain carbon dioxide and 20% carbon monoxide which
can be attributed to the reduction of carbon dioxide by colloidal aluminum metal
dispersed in the electrolyte according to the reaction:
2Al + 3CO2 = Al2O3 + 3CO
This has an effect of reducing the current efficiency
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(iii) The overall cell reaction
Al2O3 + 1.5C = 2Al + 1.5CO2
A typical electrolytic aluminum reduction cell consists of a steel lined carbon block
which serves as the current conductor to and container for the layer of reduced molten
aluminum above it which behaves as the cathode during operation of the cell. Steel
collector bars make contact with the carbon lining to conduct the electric current to the
cells. Carbon anodes are dipped into the molten electrolyte above the aluminum. As
shown by the anode reaction, carbon is consumed in the process and the anodes have to
be replaced normally in 21days. Carbon consumption varies from 0.44 to 0.49kg of
carbon per kg of aluminum produced. Aluminum is withdrawn every 3 to 4 days and is
homogenized before casting into a range of shapes.
Task
Carbon consumption is one of the major challenges in the Hall-Heroult process; the use
of permanent anodes is possible by using fused chloride electrolytes. Review any method
of electrowinning aluminum in fused electrodes.
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8.0 Nickel Extraction Processes
At the end of the section you are expected to:
Describe the extraction process of nickel from laterites with the aid of a
flowsheet
Describe the Sherritt Gordon Process
Discuss the local nickel processes with reference to the Sherritt Gordon Process
Explain the mechanisms of the processes involved
8.1 Extraction of Nickel from Laterites

Nickel laterites represent an important example of direct-leaching ores. The process
involves the use of ammoniacal ammonium carbonate leach solutions for the dissolution
of an iron-nickel alloy produced in a reductive roast pretreatment step. The leaching takes
place at atmospheric pressure with oxygenation by air and nickel carbonate is
precipitated. In various modifications, the carbonate may be reduced by coke to a highly
metallized sinter or may be simply calcined to NiO. A modification proposed by Sherritt
Gordon produces metallic nickel by autoclave hydrogen reduction. Recently, Amax
introduced a combined high-pressure and atmospheric-pressure acid-leach process
capable of treating both limonitic and garnierite-type ores. Dissolved nickel and cobalt
are precipitated as sulfides. The process consists of the following steps:
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In the process, cobalt is removed by precipitation as a sulfide containing a high Ni: CO
ratio (Ni: Co > 500). Figure 8.1 illustrates a sample flowsheet of the process.
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Figure 8.1 A sample flowsheet for the recovery of nickel from laterite ores
Task
We referred to the Sherritt Gordon process in Chapter 2, Review the process with respect
to recovery of nickel from matte. How does this process compare with nickel recovery at
BNC Refinery and ENR? Compare and contrast the two local processes? Do you see any
avenues of Improvement of the current processes?
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HYDROMETALLURGICAL PROCESSES NOTES

1.3.0 Mineral Chemistry Electrochemistry

1.3.1 The Electrode Electrolyte Interface

TASK: Elaborate this with respect to corrosion.

1.3.2 Electrochemical Potential

1.3.3 Electrochemical cells

1.3.8 Oxidation-Reduction (Redox) Electrodes

1.3.8.1 The hydrogen electrode and Standard electrode potentials

1.12.2 Electrolyte Solutions

Figure 1.1: Relationship between conductance and concentration of electrolyte.

2.1 Scope of Leaching Practice

Figure 2.1: Various paths for handling ore in leaching practice

Substituting for pH, z =3, Eo= -1.262V and aAl02-= 10-3mol.kg-1

2.3 Kinetics of Leaching

2.4 Leaching Practice

2.4.1 Leaching of Low-Grade Ores

Figure 2.5 Flow of leach liquors in copper dump leaching

2.4.2 Direct Leaching Ore

The chemical reactions involved in dissolution are

2.4.3 Leaching of High Grade Ores

Figure 2.7 Simplified flowsheet for recovery of uranium by acid leaching

Figure 2.9 Three generalized conditions for solution mining in situ

In addition to the oxidation of sulfur and sulfur compounds Thiobacillus ferrooxidans is

2Fe++ + 2H+ + O2 = Fe+++ + H2O

2.6.1.1 Separation Factor ()

Milli equivalents of ions through the resin column

Figure 3.2: Sorption breakthrough curves

3.7 Elution or Regeneration

3.9 Recent Developments in IER

4.2.1 By the formation of uncharged coordination compounds

Table 4.1 Liquid Cation Extractants

4.2.3 By solvation with ion association

Table 4.3 Common solvating extractants

4.3 Kinetics of Solvent Extraction

3. Choice of Process Configuration. The sequence of processing steps and flowsheet

4. Choice of Contacting Equipment

While efficiency is a factor in equipment selection, mechanical considerations often

5.2.1 Electrodes in electrowinning

Energy consumption = 26.8 VI / [(A/z) x 0.01(CE)] kWh.kg-1

5.2.2.2 Electrolyte circulation and agitation

5.3 Electrorefining of Metals

Anode slimes Impure

Figure 5.3 Electrorefining of copper-general flowsheet

6.1 Ore Mineralogy and Geochemistry of Gold

Table 8.1 The Redwing Mine ore

Table 8.2 The How Mine ore

6.3 The Cyanidation Process

6.3.1 The Mechanism of Cyanidation

6.4.1 Chemical enhancement of cyanidation

6.4.2.4 Intensive Cyanidation

Concentrate from Reagent addition

6.6 Recovery of gold from solutions

6.6.1 Zinc Cementation

6.6.2 Activated Carbon Adsorption

6.6.2.3.1 Factors affecting gold adsorption

6.6.2.6 Electrowinning of gold from cyanide solutions

6.7 Destruction of cyanide in gold-mill effluents

(b) INCOs SO2 process for cyanide removal

7.1 The Bayer Process

The cathodic reaction involves direct reduction of the anionic species:

8.1 Extraction of Nickel from Laterites

place at atmospheric pressure with oxygenation by air and nickel carbonate is

precipitated. In various modifications, the carbonate may be reduced by coke to a highly

metallized sinter or may be simply calcined to NiO. A modification proposed by Sherritt