EMR 3201: introduction to hydrometallurgy

MR O D CHIKATI
AIM OF THE SUBJECT

The aim of the subject is to impart to the trainee a sound knowledge of hydrometallurgy
principles

COURSE OVERVIEW

This course is to cover all basics of Hydro- metallurgical operations, theories as well as having
a reasonable overview of metallurgical performances of the hydro metallurgical plants.

COURSE OBJECTIVES

At the end of the course the student will be able to:

(1) Understand Hydro-metallurgical processing roots of most metals.
(2) Handle Hydro- metallurgical calculations
(3) Write reports and be able to interpret Hydro-metallurgical results
(4) Troubleshooting in Hydro- metallurgical plants, etc.

Table of Contents
1.O INTRODUCTION .............................................................................................................. 2
2.0 CHEMICAL FUNDAMENTALS ....................................................................................... 5
3.0 LEACHING ....................................................................................................................... 13
4.0 SOLID-LIQUID SEPARATION ...................................................................................... 35
5.0 SOLUTION PURIFICATION & ENRICHMENT ........................................................... 44
6.0 PRECIPITATION ............................................................................................................. 63
7.0 ELECTRO-METALLURGY ............................................................................................ 72
8.0 GOLD/SILVER HYDROMETALLURGY ...................................................................... 81
9.0 BASE METALS EXTRACTION ..................................................................................... 94
10.0 REFERENCES .............................................................................................................. 100

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1.O INTRODUCTION

Introduction
Two fundamentally different types of chemical reactions occur in extractive metallurgy and,
accordingly, the technology is divided into two distinct branches (hydrometallurgy and
pyrometallurgy).

Hydrometallurgy is the field of extractive metallurgy involving the use of aqueous chemistry
for the recovery of metals from ores, concentrates and recycled or residual materials. The
extractions involve the interaction of the solid phase and an aqueous phase in order to
selectively dissolve the valuable metal. A third branch of extractive metallurgy is also
recognized ie electrometallurgy. This includes processes in which electrochemical reactions
are specifically promoted and controlled by the passage of an electric current through a metal-
bearing liquid. If the liquid is a water solution, the process is hydrometallurgical in nature. If
the liquid is a molten salt, the operation being conducted at a high temperature, then it is
essentially pyrometallurgical in nature.

Hydrometallurgical unit operations

1. Feed preparation or pre-treatment

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This is necessary to render valuable mineral accessible to solvent and chemically capable of
being dissolved in it. May include the following categories;
a) Physical methods: comminution, concentration etc.
b) Chemical methods: roasting and smelting of concentrates before leaching e.g sulphating
roasting.

2. Leaching or dissolution process. Require the following; -suitable reagent.

-metal dissolved from host rock.
-dissolution process must be selective.

3. Solid-liquid separation
Done by filtration, thickening/clarification, counter current decantation (CCD) etc.

4. Solution purification/refining (enrichment). The methods below are used;

-solvent extraction (SX). -ion exchange (IX). -carbon adsorption
- The objective is to lower impurities in solution to avoid contamination of the end product.

5. Metal recovery -cementation

-precipitation
-electrowinning
-electrorefining
6. Regeneration of reagents or
recycling

Plant operation control

Metallurgical accounting Concentration
Purpose of concentration is to separate the wanted mineral from the unwanted gangue.

Concentrate (Valuable product)

Middlings (Intermediate product)

Feed Contains some valuable product as concentrate but in a more diluted
form – normally taken back for regrinding

Tailings (discarded product), contains the gangue

Mass balances and process performance

The concept of material balance is derived from the principle of conservation of mass. This
demands that, if there is no accumulation of material in a unit operation, the mass of material
that has gone into that unit must have come out of it. What goes in must balance what comes

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out. A full material balance for a circuit indicates the flow rate and composition of every
process stream in the circuit. The flow rate of material into the circuit and the production rate
of the final product should be indicated in a quantitative manner. Also, an examination of the
quality of the feed and products indicates how well each unit operation is performing.

Control variables
Grade/assay = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑛𝑡𝑒𝑑 𝑚𝑖𝑛𝑒𝑟𝑎𝑙 𝑖𝑛 𝑠𝑡𝑟𝑒𝑎𝑚 ×
100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑡𝑟𝑒𝑎𝑚

Average leach head assay

Recovery = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑖𝑛𝑒𝑟𝑎𝑙 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑒 × 100%

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑖𝑛𝑒𝑟𝑎𝑙 𝑖𝑛 𝑓𝑒𝑒𝑑 𝑠𝑡𝑟𝑒𝑎𝑚

Mass pull- mass % of feed recovered to concentrate ie = 𝐶 × 100%

𝐹

Ratio of concentration = 𝐹
𝐶

Enrichment/ upgrade ratio 𝑐 × 100%

𝑓

Separation efficiency = 𝑅𝑚 − 𝑅𝑔

Pulp density
In the processing plant, pulp density is measured by a density can on a marcy scale and also
automatic density gaunges are used. In order to calculate slurry density the mass of solids and
of water need to be known. The density is then given as;
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑖𝑑𝑠
%𝑠𝑜𝑙𝑖𝑑𝑠 = × 100%
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑙𝑢𝑟𝑟𝑦

Dilution ratio- This is the ratio of the weight of water to the weight of the solids. Can be used
to determine the amount of water in a stream.

Hydrometallurgical Extraction/ Recovery

Can be applied to hydrometallurgical units. The overall extraction/ recovery of the value metal
or mineral into the final product can be computed.

% Accountability This is expressed

as 𝑜𝑢𝑡𝑝𝑢𝑡 × 100%
𝑖𝑛𝑝𝑢𝑡

Analysis and control

Satisfactory analytical tools for both solutions and solids provide important information for
plant control. Analysis results are specific to particular plant design. Instrumental techniques
for measurement of pH and concentration have been developed and are often reliable.

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2.0 CHEMICAL FUNDAMENTALS

2.1 Solutions

Solution- is a homogeneous mixture of reagents or chemicals.

Concentrations of solutions
1. W/W weight % solution: Is concentration expressed as % of solute in a given mass of
solution. 10% NaOH means 10gNaOH in 90g of water.

2. W/V weight/volume: Concentration as grams of solute per 100ml of solution. 5% AgNO 3 is

prepared by dissolving 5g AgNO3 in water to give 100ml volume of solution.

3. V/V volume %: liquids dissolve in liquids. A concentration of 70% means mixing 70ml of
reagent with solvent and making up to the total volume of 100ml.

4. Parts per million (ppm): This is determined as follows; 𝑝𝑝𝑚 = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

× 106
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

5. Molarity(M): This refers to the number of moles per litre of solution (mol/l)

2.2 Chemical equilibria

Some chemical reactions reach completion e.g. 𝐴 + 𝐵 → 𝐶 + 𝐷
However, some reactions are reversible i.e. 𝐴 + 𝐵 = 𝐶 + 𝐷
A state of dynamic equilibrium is reached when the forward and reverse reactions occur at the
same time. Chemical equilibrium is the state in which the chemical activities or concentrations
of reactants and products have no net change over time. Forward process proceeds at the same
rate as the reverse reaction.

Equilibrium law/ Law of mass action

When a chemical reaction reaches equilibrium the concentration of reactants and products obey
the law of mass action. For a generic chemical reaction;
𝑎𝐴 + 𝑏𝐵 = 𝑐𝐶 + 𝑑𝐷

Where; A, B, C, D are chemical species and, a,

b, c, d are stoichiometric coefficients.
It follows that the equilibrium constant Kc is given as follows;

𝐶𝑐𝐷𝑑

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 𝐾𝑐 = 𝐴

𝑎𝐵𝑏

For gases Kp = 𝐶𝑐𝑎𝑃𝐷𝑑𝑏 where P is the partial pressure (Nm-2).

𝑃𝐴 𝑃𝐵
The larger the Kc the more the equilibrium favours products. Smaller Kc i.e <1, favours
reactants.
NB: Species in gases or solutions appear in equilibrium expression.
-Pure solids/liquids do not appear in the expression.
- Kc is constant if temperature is constant.
- Pressure and concentration changes does not affect Kc (Also catalyst action).

Revision Questions
Question 1; Three experiments were carried out on the following equilibrium process;
H2(g) + I2(g) = 2HI(g)
Results are shown below.

Experiment No. H2(g) I2(g) HI(g)

Equilibrium concentration x 10 (moldm-3)
-2

1 3.42 0.36 7.73

2 2.34 0.93 10.21
3 2.76 0.64 9.37

i. Using the data calculate the value of Kc for each experiment.

ii. Within experimental error, what conclusion can you draw about the value of Kc?
iii. What is a reversible raction? iv. Define dynamic equilibrium.
v. State Le Chatelier’s principle.

Question 2; Suppose two moles of H2 and 1 mole of I2 are mixed together in a 1 dm3 vessel at
440ºC. How many moles of HI, H2 and I2 will be present at equilibrium. Kc = 0.02 for the
reaction 2HI(g) = H2(g) + I2(g)

Question 3; Calculate the Kc for the following reaction occurring at 440ºC in a 1litre vessel;
2HI(g) = H2(g) + I2(g). Given that one mole of HI decompose and leave 0.78 moles of HI at
equilibrium.

Question 4; At a certain temperature and a total pressure of 10 5Pascals iodine vapour contains
40% by volume of iodine atoms; I2(g) = 2I(g)
a) Calculate the Kp for the equilibrium.
b) At what total pressure (without change of temperature) would the % of iodine atoms be
reduced to 20%.

For the reaction; CaH2(s) + 2H2O(g) = Ca(OH)2(s) + 2H2(g) Kc is given as;

[𝐻2]2

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 𝐾𝑐 = [ 𝐻2𝑂]2

The equilibrium constant for the reverse reaction Kc/ is = 1

𝐾

Ionic equilibrium (Aqueous solutions)

i. Equilibrium between an undissolved solid solute and its dissolved products in

solution i.e. solubility equilibria.
ii. Equilibrium between a dissolved undissociated molecule and its dissociated ions
i.e. dissociation equilibria (acids or bases).

Solubility equilibrium (solute-solution equilibrium)

Solubility- maximum solute that can dissolve at a given temperature in a solvent (concentration
at equilibrium).

A solute dissolves in a solvent up to a particular point at that temperature and the solution is
said to be saturated.

Sugar (s) = Sugar(aq)

PbCl2(s) = PbCl2(aq)

When equilibrium between pure AgBrO3 and its solution is reached;

AgBrO3 = Ag(aq)+ + BrO3(aq)-

[𝐴𝑔𝑎𝑞+][𝐵𝑟𝑂3−𝑎𝑞]
𝐾𝑐 =
[𝐴𝑔𝐵𝑟𝑂3(𝑠)]

[AgBrO3-(s)] is a constant. It follows that;

[𝐴𝑔𝑎𝑞+] [𝐵𝑟𝑂3−𝑎𝑞] = 𝐾𝑐 [𝐴𝑔𝐵𝑟𝑂3(𝑠)]

Constant
The constant is known as SOLUBILITY PRODUCT (KSP). In general for the reaction:

𝐴𝑥𝐵𝑦(𝑠) = 𝑥𝐴𝑦+(𝑎𝑞) + 𝑦𝐵𝑥−𝑎𝑞

𝐾𝑠𝑝 = [𝐴𝑦+]𝑥[𝐵𝑥−]𝑦

Revision Question:

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 i. Write the solubility product expression for the following;

Bi2S3; Ag2CO3; AgCl; and PbI2.

ii. A saturated solution of AgCl contains 1.46 x 10 -3g/l at 18ºC. What is the Ksp of
AgCl at this temperature?

Solution; Solubility of AgCl at 18ºC = 1.46 x 10-3g/l

= 1 .46 x 10−3 mol/l where 143.5 is the RMM of

AgCl 143.5

= 1x 10-5M

At equilibrium; AgCl(s) = Ag(aq)+ + Cl(aq)-

[Ag+] = [Cl-] = 1x 10-5mol/l

∴ 𝐾𝑠𝑝 = [Ag+][Cl-] = 10-5 x 10-5

= 10-10M2 (NB: units are important)

Solubility can also be calculated given the Ksp value. For example given the Ksp of Ag2CO3 at
20ºC to be 8 x 10-12 M3, you are required to calculate its solubility

Answer: Equilibrium is Ag2CO3(s) = 2Ag(aq)+ + CO32-(aq)

S = 1.25 x 10-4 moldm-3

NB: Ksp is valid only for saturated solutions in which the total concentration of ions is <0.01M.
If the concentration is > 0.01 then Ksp is no longer constant. For salts like NaCl, AgNO3, e.t.c.
it is inappropriate.

Physical meaning of Ksp

i. If an aqueous solution is left in contact with excesss solid Ag 2CO3 , the solid will dissolve
until; [Ag+]2[CO32-] = Ksp, thus amount of undissolved solid remains constant. Unless excess
solid remains, no guarantee that [Ag+]2[CO32-] = Ksp.
ii. Precipitation

Ag+ and CO32- are mixed such that the product [Ag+]2[CO3-] exceeds Ksp then Ag2CO3 will
precipitate. Precipitate forms when the product of ions exceeds Ksp. If [Ag+]2[CO32-] >> Ksp
then Ag2CO3 will precipitate. So Ksp helps predict maximum concentration of ions in solution,
hence determine if a precipitate forms or not.

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Problem: A 10-3 mol/l solution of Ca2+ ions is mixed with equal volume of a 10-3 mol/l solution
of SO42- ions at 25ºC. Will a precipitate of CaSO4 form? Ksp(CaSO4) = 2 x 10-3M2 at 25ºC.
−3

Solution: Before any precipitation; [Ca2+] = [SO42-] = 10 M = 5 x 10-4M

2

Ionic product after mixing; [Ca2+][SO42-] = (5 x 10-4) x (5 x 10-4) = 2.5 x 10-7M2. Ionic product
< Ksp for CaSO4 so no precipitation.

(Also consider 10-2).

NB: Can look at Ksp value and see if precipitation can be used to separate (selective
precipitation). For example separation of lead and mercury ions as PbI2 and Hg2I2 in an iodide
solution.

Revision Questions:

i. Explain the Ksp principle.

ii. Explain why precipitation is never 100% using this principle.

Common Ion Effect

A salt is more soluble in water than in a solution containing one of its ions, e.g barium sulphate
is more soluble in water than either sodium sulphate or barium nitrate.

Question: The solubility product of PbSO4 in water is 1.6 x 10-8. Calculate the solubility of
PbSO4 in;

i. Pure water. ii. 0.1

mol/l Pb(NO3)2.

Answer: i. PbSO4 = Pb2+ + SO42-

1- S S S

S2 = 1.6 x 10-8

S = 1.26 x 10-4 mol/l

ii. PbSO4 = Pb2+ + SO42-

1- S S S

Pb(NO3)2 = Pb2+ + 2NO3-

1 – S/ S/ 2S/

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 0.1 0.2

[Pb2+] = 0.1 + S

1.6 x 10-8 = [Pb2+][SO42-]

1.6 x 10-8 = S(0.1 + S) but S<<<0.1

↔ 1.6 x 10-8 = 0.1S

∴ 𝑆 = 1.6 x 10-7 mol/l

Revision Question: Ksp of silver carbonate at 20ºC is 8 x 10-12. Calculate its solubility in;

i. Water.
ii. 0.01M AgNO3. iii. Compare i. and ii. and
state the name of the effect.

Hydration
Attachment of polar water molecules to ions. When NaCl dissolves in water, the crystal lattice
is broken down forming separate Na+ and Cl- ions in aqueous solution. Ion-solvent bonds
formed provide the energy.
Solvation of ions occur;
- -

+ +
+ +

- -

NaCl(s) water Na+(aq) + Cl-(aq)

Hydrolysis

Breaking into two new compounds. It is the decomposition of a chemical compound by the
reaction with water, such as dissociation of a dissolved salt.
Cr2O72- + H2O = 2CrO42- + 2H+

CN- + H2O = HCN + OH-

Acid hydrolysis

MO + 2H+ = M2+ + H2O

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ZnO + 2H+ = Zn2+ + H2O

Reagent normally used is sulphuric acid on metallic oxides or hydroxides which easily
dissolve.

Base hydrolysis

Al2O3 + 2OH- + 3H2O = 2Al(OH)4- used for amphoteric metals e.g. Pb, Cu, Al, Zn e.t.c.

Acid – Base reactions

Neutralisation- process of acid reacting with a base/alkali forming water. For example;

HCl + NaOH = NaCl + H2O

Cu(OH)2(s) + 2H+(aq) = Cu2+(aq) + H2O

Buffer solutions

A buffer is a solution that resists changes in pH on addition of small amounts of acid or alkali.
A buffer is made up of;

i. A weak acid and its salt ( e.g. ethanoic acid and sodium ethanoate). ii.
A weak base and its salt (e.g. ammonia and ammonium chloride).

Uses
-pH meter calibrations.

-To identify pH of unknown solutions.

- Maintain constant pH in leaching.

- In electroplating processes.

Redox reactions
Reactions involving reduction and oxidation processes. Can be considered in terms of oxygen,
hydrogen, electrons and oxidation number changes.

(Revise rules used in assigning oxidation state).

Problem: Assign oxidation numbers to the following ions; UO2+, BrO3-, OF2, CaH2, U3O8, ClO4-
and Fe3O4.

Examples of oxidation reactions include;

a) Reactions of metals with non-metals.

b) Reactions of metals with water/steam.

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 c) Reactions of metals with acids.
d) Reactions at electrodes during electrolysis

Some metals react with oxygen for example magnesium react as shown below;

2𝑀(𝑠) + 𝑂2(𝑔) → 2𝑀𝑔𝑂(𝑠)

The metal is oxidized, and oxygen is reduced, i.e. the half equations are as follows;

i. 2𝑀 → 2𝑀𝑔2+ + 4𝑒− ii. 𝑂2

+ 4𝑒− → 2𝑂2−

These chemical reactions should be balanced. Iron reacts with HCl acid to produce a salt and
bubbles of hydrogen gas. Fe + 2HCl = FeCl2 + H2. Iron is oxidized, hydrogen is reduced
and the chlorine ion does not change its state (spectator ion). If iron is replaced with platinum
the following is noted;

 No reaction.
 No hydrogen evolution.
 No platinum ions in solution.

If iron and platinum are simultaneously exposed to the acid, the two electrically connected,
hydrogen is evolved on the surface of platinum.

Fe = Fe2+ + 2e- (metal)

(soln) (metal)

2H+ + 2e- = H2

(solution) (metal) (gas)

NB: Anodes are locations where electrons are being generated/given up and cathodes are sites
where electrons are consumed/discharged. For electrochemical dissolution, there must be an
electrochemical cell.

Components of the electrochemical cell

 Anodic sites.
 Cathodic sites.
 Electrical contact between anodes and cathodes.
 Conducting electrolytic solution.  Cathodic reactant.

Anodic reactions in metallic dissolution relatively simple. Always such that metal is oxidized
to a higher valence state.

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M = Mn+ + ne-

Where: M- is metal/species undergoing oxidation.

Mn+- is metal ion.

ne-- number of electrons lost.

Cathodic reactions are difficult to predict, but can be;

a) Hydrogen evolution, 2H+ + 2e- = H2

b) Oxygen reduction in acid, O2 + 4H+ + 4e- = 2H2O
c) Oxygen reduction in neutral solutions, O2 + 2H2O + 4e- = 4OH-
d) Metal ion reduction, M3+ + e- = M2+
e) Metal ion deposition, M2+ + 2e- = M

3.0 LEACHING
Involves contacting a solid phase, e.g. ore or concentrate, with an aqueous solution of the
leaching agent in order to dissolve the value mineral(s). On the other hand, gangue minerals
can be dissolved leaving value minerals on the solid phase in what is known as
“hydrometallurgical beneficiation”. Lixiviant/leachant
Leaching agent e.g. acids, salts e.t.c.

Choice of lixiviant
a) Rate of reaction- must dissolve mineral fast enough.
b) Selectivity.
c) Cheap and readily available in large quantities.
d) Ability to be regenerated/recycled.
e) Mineralogy and chemical composition of ore.

Factors affecting selectivity of a lixiviant

 Concentration- Excess lixiviant concentration would dissolve other minerals. For

example in the leaching of copper oxide ores, acidity should be controlled to avoid
dissolution of undesirable minerals.
 Temperature- Sometimes little effect on leaching efficiency but an increase in
temperature can increase impurity levels. Cooling may be necessary to optimize
temperature. For copper oxide ore an average temperature of 29.5ºC is used.
 Residence time/contact time- extended contact time between the solvent and ore may
result in a high dissolution of impurities. In sulphuric acid leaching of copper oxide
mineral, copper mineral dissolves first. Continued contact result in iron and
aluminium minerals dissolving as feldspars and sericites slowly breaking down under
the acid. Therefore, minimum contact time resulting in maximum copper recovery
and minimum impurity contamination should be selected.

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Leaching variables of processing

1. Particle size/surface area. This imposes a major limit on the extraction rate and ultimate
recovery. Typical leach feed size include;

Gold (associated with sulphides): 200 mesh (-75 µm).

Bauxites : 100mesh (-150µm). Uranium ores : -500µm.

Effects of grinding on metal extraction

Extraction/dissolution
reaches a plateau

Economic limit of grinding

Decreasing particle size

Economic limit is usually defined as the point at which the cost of grinding is not covered by
greater extraction or increased extraction is countered by increased reagent consumption.

2. Reagent concentration- operator controlled variable. Optimization of reagent dosage and

strength is important in minimizing consumption and maximize extraction. Principally
because reagent costs form the bulky of leaching costs. Dosages experimentally determined
for each particular ore.
3. Oxygen and other gases. May be involved in the leaching reaction. Solubility of gases
markedly depended on temperature. Oxygen at 25ºC and 1atmosphere is 8.26mg/l while
for pure oxygen at the same conditions is 40.3mg/l. Both values decrease with an increase
in temperature. In agitation leaching compressed air used to increase oxygen concentration.
Pressurized air is used in the oxidative leaching of NiSO4.

4. Temperature- increases leaching rates e.g. oxidative leaching of nickel sulphides

concentrates. The relationship between rate of reaction and temperature is shown by the
equation;

−𝐸𝐴

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 𝑘 = 𝐴𝑒𝑥𝑝 { }
𝑅𝑇

Where: EA is activation energy.

R- is gas constant (8.314j/mol).

T- temperature (kelvins).

A- Arrhenius constant.

An increase in temperature results in a decrease of viscosity and an increase on the kinetic

energy of reacting species.

diffusion controlled

chemically controlled

temperature
Diffusion controlled reaction: rate α temperature (E A < 20 kj/mol). For chemically controlled
reactions, the rate increases exponentially with an increase in temperature (E A > 20kj/mol).
Mixed control reactions have EA between 20 and 40 kj/mol.

5. Effect of pressure. Effects of pressure applies where a gas is involved in the reaction e.g.
cyanide leaching of gold. In compressed air agitation, the transfer of oxygen from air into
solution is maximized. Another example is the oxidation of sphalerite in the ‘Comico
Process’. ZnS + H2SO4 → No reaction

ZnS + H2SO4 + 0.5O2 → ZnSO4 + H2O + S

400ºC
Oxidation of pyrite; FeS2 + O2 + H2O Fe2(SO4)3 + H2SO4
15 bars

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6. Agitation/stirring rates.

Economic limit

Stirring rate

Limiting point often realized in diffusion controlled processes. In most cases, stirring rate
must be sufficient to prevent settling (siltation). A stirring rate that maximize dissolution
must be used.

NB: Regions close or adjacent to the mineral surface must not be depleted of the lixiviant.
Agitation increases mass transfer of gases to the liquid-solid interface.
7. Pulp density- lower pulp density high kinetics because mass transfer easy. This results in
homogeneous mixing. Low density also saves agitation energy. Pulp density to be used
depend on; particle size of feed, thickening capacity, dilutions, type of ore, availability of
lixiviant, type of lixiviant and desired build up of metal in solution.

8. Pulp viscosity- this is the resistance to flow of pulp. Not normally an important factor in
ore leaching. In agitation, percolation and most leaching methods, there are difficulties in
handling high clay ores. They are sticky and oxygen might not go through.

9. Product of leaching. The product must be stable. Products may revert back to the original
form or may further react with reagents. Some products may form a coating or insulating

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 film on the mineral surface. This prevents movement of reactants and products to and from
the surface. Sulphur is an example in the following reaction;

2ZnS(s) + O2 + 4H+ = 2Zn2+ + 2H2O + 2S(s)

10. pH- some leaching reactions are affected by changes in pH.

Thermodynamic Aspects of leaching

The Eh-pH diagram

- Also called the Pourbax diagram.
- The Eh-pH diagram is a graphical representation of thermodynamic data as a function
of potential (E) and pH.
- Indicate thermodynamically stable phases as a function of electrode potential and pH.
- Used to predict general conditions likely to be favorable to mineral dissolution.
- Metal-water system yield simplest diagrams at 25ºC and 1 atmosphere.
- Activity used for;
i. Corrosion systems is 10-6M
ii. Hydrometallurgy is 10-2M or 10-3M

- Establishment of boundaries results in formation of domains. A particular species is

thermodynamically stable in each domain (region).

Hydrogen Equilibrium:

2𝐻+ + 2𝑒− ⇌ 𝐻2

𝐸 = 𝐸𝜃 + 𝑅𝑇 ℓ𝑛 [𝐻+2]2
2𝐹 [𝐻 ]

Electrochemical reactions of 𝑯𝟐𝑶

At high potentials a 2nd reaction possible; oxygen evolution.

2𝐻2𝑂 ⇌ 𝑂2 + 4𝐻+ + 4𝑒−

Both pH and potential dependent.

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 2
x
𝑂2 evol
Y
𝐻2 stability
E(v) region
Z 𝐻2 evol
-2

0
pH 14

Note points:
- Reactions that do not involve charge transfer are independent of pH.
- The vertical line is acid-base equilibrium.
- Horizontal line is redox equilibrium.
- Slanting line represents both acid-base and redox equilibrium.
- Any point gives the thermodynamically most stable or most abundant form of the
element at a given potential and pH conditions.
- Strong oxidizing agents are found at the top of the diagram.
- Reducing compounds are found at the bottom of the diagram.
- When the predominance area for a given oxidation state disappears completely above
or below a given pH and the element is in an intermediate oxidation state, the element
would undergo disproportionation.
- A species that ranges from the top to the bottom of the diagram at a given pH would
have no oxidizing or reducing properties at that pH.

Zinc-Water system

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 1.23
1
Zn2+
ZnO
0 ZnO22-

-1

-2

0 4 8 pH 12
2+
- The reaction of Zn forming ZnO would depend on pH.
- The equilibrium of Zn to Zn2+ is a redox reaction.
- Slanting line represents pH and redox dependant reactions.
- Zinc dissolution essentially electrochemical.
- Zinc reduction more negative than both water boundary reactions. Both reactions can
act as cathodic reactions.

Water system lines of equilibrium

O2 + 4H+ + 4e = 2H2O
2H+ + 2e = H2 ( or 2H2O + 2e = H2 + 2OH-)
Potential more negative (more reducing) than the lower boundary, water decompose giving
hydrogen.

Zn2+ + 2e = Zn anodic
2H+ + 2e = H2 cathodic
Zn + 2H+ = Zn2+ + H2 Overall

- Dissolution favorable below pH 6.9 with the formation of Zn 2+, also above pH 13.4
with ZnO22- formed.

Copper-Water system
Leaching reaction is Cu = Cu2+ + 2e 0.34V
It has a more positive potential than the hydrogen evolution reaction. Dissolution occurs at pH
less than 7 and is only supported by the oxygen reduction reaction.

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Gold-Water system

The reaction for the dissolution of gold has a very high positive value such that its noble in
most common acidic or alkaline reagents i.e. its above the water line. However the formation

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of a complex lowers the potential value which makes it possible to dissolve gold in alkaline
solutions.

Copper-Cyanide-Water system

CuO
1.23
1 Cu2+
CuCN32-
0 CuCN43-
CuCN2-

-1
Cu HCN CN-
-2

0 4 pH 8 12

- The pourbaix diagram for the copper-cyanide-water system indicates that copper
dissolution can be achieved by either oxygen reduction or hydrogen evolution acting
as cathodic reactions. The dissolution domains have been extended especially in the
alkaline region.

- Presence of complexing agents can considerably modify E-pH diagrams for metalwater
system due to the formation of highly stable complex ions.
- Gold is highly susceptible to complex ion formation and in particular it readily forms
the Au(CN)2- complex ion.
- Au(CN)2- + e = Au + 2CN- Eo = -0.61V Au3+ + 3e = Au
o
E = +1.45V

- This value show the drastic (Eo = -0.61V) shift from the highly positive Eo value of
Au3+ + 3e = Au.
- The potential is sufficiently negative to allow either oxygen reduction or hydrogen
evolution to act cathodically for gold dissolution.
- Oxygen reduction more effective and used.

Limitations of Pourbaix diagrams

- Derived at a particular temperature and pressure.
- Relate only to stable species but meta-stable states often occur in practice.
- Are only defined for pure metals but alloys are considered often in practice.
- No information on reaction kinetics only possibility of a reaction. - Are for
selected concentration of ionic species.

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Leaching Processes
Leaching processes can be categorized as;
i. Non-oxidative (Chemical and Reductive)
ii. Oxidative

Chemical dissolution
- It does not involve electrons.
- It is commonly encountered in metal oxide dissolution e.g. aluminium-water system.
- Al2O3 (bauxite) is chemically capable of dissolving in either acid or alkaline medium.
- Al2O3 + 6H+ = Al3+ + 3H2O acid medium Al2O3 + OH- = 2AlO2-
+ H+ alkaline medium

- Both reactions have been used in extraction of Al, H2SO4 acid leaching of bauxites have
been utilized but alkaline leaching is almost exclusively practiced.
- In the Bayer process leaching of high grade bauxite is carried out with aqueous NaOH
at elevated temperature and pressure to give high rate of dissolution.

The Bayer process

- Involves the dissolution of aluminium minerals in aqueous NaOH.
- Al(OH)3 + NaOH = NaAlO2 + 2H2O AlO(OH) + NaOH = NaAlO2
+ H2O

Parameters; NaOH concentration, 3 to 12M; temperature 140 to 180ºC; time 1 to 4 hours

- Iron oxides mainly Fe2O3 and quartz remain insoluble during leaching.
- Any silica combined with alumina (kaolinite) dissolves and give NaAl-Silicate (Red

Mud). A loss of aluminium from the circuit.

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 - Filtration is done then solution diluted and fresh Al(OH) 3 added to bring about
hydrolytic precipitation of aluminium.

NaAlO2 + 2H2O = Al(OH)3 + NaOH

- Precipitate filtered and calcined to Al 2O3 at 1100ºC and NaOH recycled.

Uraninite (UO2) dissolution

1.23
1
UO22+ UO3

4+

3+

0 U 3O8
U

-1
U UO2

-2

0 4 8 pH 12

- The diagram shows that all three types of dissolution are feasible for uraninite (UO 2).
- Chemical dissolution equilibrium; UO2 → U4+ no change in oxidation state. The
reaction is pH dependant.
- An acid (non-oxidising) is required to facilitate the dissolution.
- In the reductive dissolution from UO2 → U3+, reaction is;
UO2 + 4H+ + e = U3+ + 2H2O a strong reducing agent is required and this would
decompose water, so the reaction cannot be used.
- In oxidative leaching; UO2 → UO22+, an acid solution containing ferric salts is usually
practiced e.g. UO2 + Fe2(SO4)3 = UO22+ + 2FeSO4
- In simple terms; Fe3+ + e = Fe2+
UO2 + 2Fe3+ = UO22+ + 2Fe2+

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 - The process yields uranyl ions (UO22+) suitable for subsequent separation processes e.g.
ion exchange.
- U3O8 shows that only oxidative dissolution is possible e.g. U3O8 + 4H+ = 3UO22+
+ 2H2O + 2e
- Carbonate and hydrogen carbonate can be used;
i. UO3 + CO32- + HCO3- = UO2(CO3)34- + H2O ii.
UO2 + 0.5O2 = UO3

Chemical leaching of oxidized copper ores

Copper sulphides capped by oxidized minerals e.g. azurite, malachite, chrysocolla, brochantite,
can be leached using heap, vat or agitation methods.

Reductive Leaching
For example pyrolusite (MnO2) dissolution in dilute H2SO4 acid with SO2.
Electrochemical dissolution occurs;
MnO2 + 4H+ + 2e = Mn2+ + 2H2O cathodic
2- +
H2SO3 + H2O = SO4 + 4H + 2e anodic
2+ 2-
MnO2 + H2SO3 = Mn + H2O + SO4 overall

Filtration is done as a solid-liquid separation step and then electrowinning.

Oxidative leaching
- Oxygen and ferric salts most important oxidizing agents. Other oxidizing agents
include, CuCl2 and chlorine.
- Regeneration of Fe3+ by oxygen or MnO2 and NaClO3 (secondary oxidants).
- Bacteria also used to support oxidative leaching of minerals. They also require oxygen.
- Electrolytic anodic oxidation can be done where an external source of power is used to
re-oxidise the oxidant.

Question
1. Show whether it is possible from a thermodynamic point of view to leach native copper and
covelite (𝐶𝑢𝑆) using 𝐹𝑒3+ salts as lixiviants.
2. What conditions would promote dissolution of both 𝐶𝑢 and 𝐶𝑢𝑆.

𝐹𝑒3+ + 𝑒− = 𝐹𝑒2+ 𝐸∅ = 0.771𝑉

𝐶𝑢2+ + 2𝑒− = 𝐶𝑢 𝐸∅ = 0.34𝑉

𝐶𝑢2+ + 𝑆 + 2𝑒 = 𝐶𝑢𝑆 𝐸∅ = 0.59𝑉

Electrochemical Nature of Leaching
- Where electrons are involved, the equilibrium is electrochemical in nature and normally
dissolution is anodic.
- Oxidative leaching is regarded as electrochemical cell where anodic process is sustained
by suitable cathodic process.

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 - Potential difference between anode and cathode in an electrochemical cell originates
from thermodynamics of electrode reactions involved.

𝜖𝑐𝑎𝑡ℎ − 𝜖𝑎𝑛𝑜𝑑 = 𝜖𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛

- Faraday related p.d. with free energy;

Δ𝐺 = −𝑛𝐹𝜖 (ia)
ΔG – free energy change
𝑛 − number of electrons transferred
F – charge transported by one mole of 𝑒− (96 496 𝐶 𝑝𝑒𝑟 𝑚𝑜𝑙)

- For a spontaneous reaction Ε must be positive.

Δ𝐺𝜃 = −𝑛𝐹𝐸𝜃 (iib) standard conditions.

- Dissolution reactions are temperature depended since free energy states of the species
involved are also temperature dependent.

- So to determine Δ𝐺 at temperature other than standard make use of thermodynamic

relationship;

Δ𝐺 = Δ𝐺𝜃 + 𝑅𝑇 ℓ𝑛 𝐽 (ii)

𝑅 − gas constant (𝐽𝐾−1𝑚𝑜𝑙−1)

𝑇 − temperature (Kelvin)

𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷

𝐽= [𝐶]𝑐 [𝐷]𝑑𝑏 (iii)

[𝐴] [𝐵]

- J contains arbitrary values that correspond to non – equilibrium free energy change,∆𝐺.

- If system reaches point where there is no net change of G, it is in equilibrium hence Δ𝐺

= 0, then J = K the equilibrium constant. ∴ at equilibrium;

Δ𝐺𝜃 = −𝑅𝑇𝐼𝑛 𝑘

- Consider leaching of 𝑍𝑛𝑂 by 𝐻2𝑆𝑂4;

𝑍𝑛𝑂 + 2𝐻+ ⇌ 𝑍𝑛2+ + 𝐻2𝑂 substitute for J in (ii)

⇒ ∆𝐺 = Δ𝐺𝜃 + 𝑅𝑇ℓ𝑛 [𝑍𝑛2+2+2] (iv)

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 [𝐻 ]

- Driving force for dissolution of 𝑍𝑛 by 𝐻2𝑆𝑂4 acid is Δ𝐺 that is available and can be
determined using (iv).
- Relationship between Δ𝐺 and 𝐸 can be established by substitute equilibrium (i) b into
(iv);

−𝑛𝐹𝐸 = −𝑛𝐹𝐸𝜃 + 𝑅𝑇ℓ𝑛 𝑎𝑧𝑛2+

𝑎𝐻+ 2

𝐸 = 𝐸𝜃 − 𝑅𝑇 ℓ𝑛 𝑎𝑧𝑛2+ Nernst Equation.

𝑛𝐹 𝑎𝐻+ 2

- Consider the reaction;

Ox + e = Red

E = Eo + RT/nF In [Ox]/[Red]

E = Eo + RT/F In[Ox]/[Red]
- As the reaction proceeds, E will decrease unless ratio [Ox]/[Red] maintained by some
means.
- Secondary agents can be used to re-oxidize reduced species e.g. anodic re-oxidation.
- Alternatively the oxidant may be continuously supplied as in the case of a gas such as
oxygen or chlorine.

Galvanic interactions
Several minerals occur in one ore body, mineral particles which exhibits different potentials
and electrical conductivity form a galvanic cell or couple when they come into contact in the
solution, e.g. pyrite and sphalerite.

FeS2 = Fe2+ + 2S + 2e Eo = +0.75V ZnS

2+ o
= Zn + S + 2e E = +0.174

Cathodic mineral remains inert but not always, sphalerite will dissolve on a pyrite surface
according to the reaction;

ZnS + 0.5O2 + 2H+ = Zn2+ + S0 + H2O

Limitations of thermodynamic data

- It only indicates the tendency of the reaction to occur.
- It provides no information on reaction rate.
- It provides no information on reaction mechanism.
- Does not explain effect of unknown chemical composition of solid or liquid products
and different local solution conditions.
- The porous product layers may allow further reactions to take place.

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Kinetic considerations
Leaching is a heterogeneous process involving;
i. 2 phases; liquid-solid

iii
Solid liquid Gas

ii. 3 phases; liquid-solid-gas

ii

iv

Stage( i); Transfer of gaseous reactant from gaseous phase to and dissolution in solution.
Stage (ii); Transport of the reactant through the solution to the solid-liquid interface. Stage
(iii); Reaction at interface chemical or electrochemical and may involve adsorption and
desorption and in the case of electrochemical reaction transfer of electrons and ions across an
electrical double layer.
Stage (iv); Transport of a product from the interface into the bulk of the solution. Stage
(v); Products in gaseous phase.

Possible for any one of these reactions to be slowest (rate determining) and control rate of
overall process.

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Stage ii and iv mostly rate determining step each of which involves diffusion.
Processes of this type are diffusion controlled.
However, sometimes no single step is rate controlling, more than one stage in determining
overall rate of reaction.

Stage 1
O2(g) = O2 (aq)
Ksoln = [O2sol]/ P O2 ∴ P O2 α [ O2(aq)]
- An increase in gaseous pressure of P O2 is α to increase in dissolved oxygen
concentration in solution.
- Oxygen solubility increase with an increase in partial pressure and also vigorous
agitation.
- Temperature decrease solubility.

Stage 2
- Transport of reactants to solid-liquid interface.
- It involves passage through a diffusion layer in which the concentration of the reactant
diminishes with decreasing distance from surface due to reaction at interface.
- It obeys Fick’s 1st law of diffusion (also Nerst model).

Fick’s 1st law;

𝑑𝑛 𝑑𝑐
𝑑𝑡 = −𝐷𝐵 𝐴 𝑑𝑥

dn- number of moles of substance

B. dt- time interval. A- Area of the
plane
-dc/dx – concentration gradient
DB- diffusion coefficient (diffusivity)

CR
diffusion

CRO

Distance from surface

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 - From the graph which illustrates the difference between the assumed linear
concentration (broken line) and concentration (continuous line), it is seen that;

𝑑𝑐 𝐶𝑅 − 𝐶𝑅𝑂
−( ) =
𝑑𝑥 𝑅 𝛅

Substituting into Fick’s 1st law;

𝑑𝑛 𝐶𝑅 − 𝐶𝑅𝑂
( ) = 𝐷𝑅𝐴
𝑑𝑡 𝑅 𝛅

- The rate of flow will attain a limiting value when the solution immediately
adjacent to the solid-liquid interface is totally depleted of reagent, i.e. C RO = 0
and
𝑑𝑛 𝐷𝑅𝐴𝐶𝑅
( ) =
𝑑𝑡 𝑅 𝛅
- This indicates that a diffusion controlled reaction the rate is directly
proportional to the concentration of reagent in the bulky of the solution,
interfacial area and to the value of diffusivity whilst it is inversely proportional
to the thickness of the diffusion layer.
- Diffusivity is temperature dependant and follows the equation; D R = DROexp{-
EA/RT}
- Increase in DR with temperature is relatively small and results in low activation
energy and is approximately 20KJ/mol.

Stage 4
Transport of reaction product away from interface may also involve diffusion and can be
treated in similar way to stage by application of Fick’s 1st law.

diffusion

CP

Distance from surface

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 - Stage four become rate controlling when an insoluble layer of porous reaction product
forms on reaction surface e.g. ammonical leaching CuFeS2, NiFeS2 and Fe2O3.H2O will
be formed.
- As a result the diffusion of both the reactants to the reaction interface and products away
from it may be considered hampered.
- Once an insoluble film has been formed, diffusion through it generally becomes rate
controlling.
- As dissolution proceeds, the insoluble layer thickens with simultaneous shrinking of the
core and rate of reaction diminishes in proportion to the thickness of the soluble layer.

Stage 3
Described in terms of conventional absolute reaction rate theory involving the energy barrier
concept with intermediate formation of an activated complex.

Stage 5
- Does not affect rate of reaction.
- Can be promoted by varying temperature and pressure.

Leaching Reagents
- Acids, bases, water, salt solutions and bacteria

a. Acid Leaching
- Acids e.g. dilute H2SO4 for oxidized copper and zinc ores.
ZnO + H2SO4 = ZnSO4 + H2O
CuCO3.Cu(OH)2 + 2H2SO4 = 2CuSO4 + CO2 + 3H2O

b. Bases Leaching (Alkaline Leaching).

- NaOH (bauxite leaching); NH4OH + O2 or NH4CO3 + NH4OH for leaching CuCO3.
- Al2O3 + 2NaOH = 2NaAlO2 + H2O

Advantages of bases
- Negligible corrosion problems.
- Can be used to leach ores containing carbonates as gangue content.
- More selective, i.e. they would not leach iron which is a problem in acid leaching.

c. Water Leaching
- For example CuSO4, ZnSO4 leaching (most sulphates are water soluble).
- Under pressure at 150ºC in water medium the following reaction occurs; NiS
+ 2O2 = NiSO4(aq)

d. Bacteria Leaching
- Bacteria leaching is a mineral oxidative dissolution brought about by the acidophilic
bacteria, thiobacillus ferro-oxidans and thiobacillus thio-oxidans.
- The reactions which occur are;

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 2FeS2 + 7O2 + 2H2O = 2Fe2+ + 4H+ + 4SO42- Followed
by;
2Fe2+ + 0.5O2 + 2H+ = 2Fe3+ + H2O

- The reactions normally slow but thiobacillus ferro-oxidans capable of promoting latter
reaction at a notably high rate.
- Fe3+ resulting from bacteria oxidation promote the dissolution of a range of sulphides
and related minerals.
- Bacteria sustain leaching cycle by continuous regeneration of Fe 3+ ions.
- Elemental sulphur oxidation provides energy for the thiobacillus thio-oxidans and
S2O32- and hence sulphur forms H2SO4 acid, lowering pH conditions.
2S + 3O2 + 2H2O = 2H2SO4 -
Reaction, Fe2+ → Fe3+ require this acid.
- Thus bacteria activity forming Fe3+ promotes dissolution of sulphides and other
minerals.
- Conditions are; low pH, adequate oxygen and a temperature < 50ºC (optimum 35ºC).

e. Salts
- Includes; NaCN, KCN, NaCl, Fe2(SO4)3, CuCl2 e.t.c
- PbSO4 + 2NaCl = Na2SO4 + PbCl2

Cyanidation (Au and Ag)

- The dissolution of gold and silver in the presence of oxygen, in alkaline cyanide
solutions is termed cyanidation. - Gold dissolves anodically;
4Au + 8CN- = 4Au(CN)2- + 4e -
Oxygen reduction is cathodic reaction.
O2 + 2H2O + 4e = 4OH-
- Overall reaction is;
4Au + 8CN- + O2 + 2H2O = 4Au(CN)2- + 4OH-

Mechanism of Cyanidation
- Cyanidation is a heterogeneous reaction at solid-liquid interface involving the following
sequential steps;
i. Adsorption of oxygen in solution.
ii. Transport of dissolved cyanide and oxygen to the solid liquid interface.
iii. Adsorption of the reactants cyanide and oxygen on the solid
surface. iv. Electrochemical reaction.
v. Desorption of soluble gold-cyanide complexes and other reaction products from the
solid surface.
vi. Transport of the dissolved products into the bulk solution.

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 Aqueous phase

cathodic area O2, H2O

mineral surface CN- anodic area

Electrons Au(CN)2-

O2 + 2H2O + 2e =
H2O2 + 2OH- H2O2, OH-

(O2 + 2H2O + 4e =
4OH-)

Nernst boundary layer

Leaching Technology

Methods of leaching

Heap and dump leaching

- Similar in operation but differ in type and amount of material being leached.
Heap Leaching
Method used for low grade ores. The ore is broken and piled into relatively small heaps on
impervious ground (prepared pads). Ore can be crushed if necessary say to D80 – 200mm. The
solution with leaching reagent is sprinkled on top of the heap in case of gold ores. The lixiviant

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percolates into the ore and dissolution occurs. The pregnant solution is collected in collecting
ponds through pipes. Recovery rates are around 50% in several months.

Dump leaching
- Applied mainly to mine waste and low grade copper ores. At a large scale and often
consist of stripped material adjacent to main ore body of value minerals.
- Leach solution fed periodically by sprays over the dumps or through perforated pipes
into the material.
- Recovery is 50% in one to two years.

Percolation leaching
- Also known as vat leaching or sand leaching.
- For relatively low grade ores of coarse particle size 10mm (sandy or porous ore).
- Method not well suited for material which tend to pack into impervious masses.
- Material to be leached is placed into large false bottomed tanks or vats which are lined
with lead or asphalt to resist corrosion.
- The false bottom is covered with a filter medium.
- Solution added to top of tank and allowed to percolate through the ore. A counter current
system is generated by configuration of the tanks. After contacting for a certain time,
solution is drained and fresh solution added.
- First a weak solution of solvent and finally leaching with a stronger solution being used.
After leaching cycle is complete, tailings are removed and tanks emptied.
- Can be batch or continuous.
- Recovery is 80% in one week.

Agitation leaching
- Also called slime leaching.
- Carried out on finely ground ore (< 0.5mm usually 70-100µm) in steel tanks or Pachuca
tanks.
- Agitation is by mechanical impellers or compressed air.
- Agitation minimizes diffusion-layer thickness and in gaseous reactants maximizes gas-
liquid interfacial area.
- Recovery >90% 4 to 8hours.

In-situ leaching
- In-situ leaching also referred to as solution mining or in-place leaching.
- Leaching of mineral deposit within the earth’s crust without prior removal.
- Low grade ores remaining within worked-out mines and to recovery metals directly
from ore bodies within the ground where convectional mining techniques would be
uneconomical e.g. mine water for leaching CuSO4.
Injection in situ leaching

- The process done in buried ore body where lixiviant is injected through a
perforated injection well into the ore body which is shattered to facilitate
lixiviant penetration during leaching of valuable minerals.

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 - A pump installed underground facilitates the recovery of pregnant solution
from the collection well to the processing plant for further treatment.

Developing a Leaching processing route

i. Examination of the ore

- To determine mineralogical, chemical and physical properties.

- Mineralogical examination helps get grain size distribution (evaluated by comminution
tests).
- Helps identification of associated gangue minerals and hence appropriate choice of
lixiviant.

Chemical analysis

- To determine assay or grade of ore. Helps to know concentration of lixiviant to use. -

Also reveal constituents of ore e.g. lead content.

Physical properties

- Ore porosity, specific gravity, tumbler strength and hardness need to be determined.
- Helps in choice of leaching method e.g. if ore is porous and relatively strong, heap
leaching possible. ii. Laboratory tests

- Conducted basing on ore examination results.

- Percolation tests can be done to determine optimum leaching time.
- Agitation test work can also be performed using pneumatic or mechanical agitators.
- Variation of process parameters done, i.e. pH, temperature, residence time and agitation
rate.

iii. Lixiviant chosen basing on mineralogy and physical properties of ore, for instance
if ore contains a lot of carbonates a basic lixiviant is opted for.

iv. Metal recovery from solution is evaluated basing on quantity and type of ions
present.

- If pregnant solution contains low impurities then electrowinning can be done.

- Solvent extraction tests can be done and extractants chosen basing on distribution
coefficients determined.
- Ion exchangers can be used to adsorb metals of interest from the solution and eluate
them as required.
- Preferred when no other ions of chemical equivalence to the required metal are present
in the solution.

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 v. Optimization of residence time, concentration, pH, agitation rate e.t.c of the above
processes done and the best route selected which provides the efficient and
economical way of metal recovery.

4.0 SOLID-LIQUID SEPARATION

Introduction
- The pregnant leach solution has to be separated from the insoluble gangue and the
water-solid ratio may be high.
- Solid-liquid prepares the solution for subsequent metal recovery.
- It is common to practically all mineral processing operations as the bulk of beneficiation
plants employ water as the major processing vehicle.
- The growing usage of hydrometallurgy has increased the importance of solid-liquid
separation as acidic and basic solutions result in greater difficulty of operation, the
economic need for chemical recovery to minimize this operating cost and the usual
necessity to employ more costly construction materials.
- Solid-liquid separation usually done by sedimentation and filtration.
- Sedimentation favored when there is a large density difference between the solids and
the liquid.
- However, it cannot be applied always in hydrometallurgical processes because in some
cases a high grade leach liquor may have a density approaching that of the solids.

Sedimentation
Is the removal of suspended particles from a liquor stream by gravity settling. It has two main
applications i.e. clarification and thickening.
i. Clarification- remove a relatively small quantity of suspended particles and produce a
clear effluent or overflow. Separation characterized by sediment without a clearly defined
interface between clear liquid and sediment. Primary interest is in the quality of the liquid as
the end product.
ii. Thickening- increase the concentration of a relatively large quantity of suspended solids
in a feed stream. It is characterized by a clear liquid-sediment interface. Emphasis is on solids
as the end product of separation in order to facilitate subsequent processing or disposal of
solids.

The thickener is used to increase the concentration of suspended solids (thickening)

accompanied by the formation of a clear liquid (clarification). Centrifugal sedimentation may
be done to enhance the settling rates. Alternatively, particles can be agglomerated or
flocculated into relatively large lumps (flocs) that settle rapidly.

Flocculation
Flocculation relies upon molecules of a reagent acting as bridges between separate suspended
particles. The reagents are long chain organic polymers which were formerly natural minerals,
e.g. starch, glue, gelatine and guar gum (polyelectrolytes). Polyacrylamides are extensively
used as flocculants. Repulsion forces also hinder settling as particles are in constant motion.

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Flocculants are used to bring about adhesion of particles. These form many interparticle
bridges, whose strengths depends on the efficiency of adsorption of the polymer on the surface.

Excessive agitation can result in breakdown of flocculants. Flocculating agents are not very
successful in hydrocyclones. Even pumping of flocculated slurry may destroy flocculants
(rapture of long chain molecules).

Addition of flocculants must be made at several points to ensure adequate spread of the
flocculant. Mild agitation is essential at addition points. Severe agitation after the flocculants
have been formed must be avoided. Some of the flocculants in use include anikem, magnafloc,
anionic 345, cationic 368 and yang-floc.

Selective Flocculation
This occurs, when a mixture of minerals is dissolved in pulp and the flocculant selectively
adsorb one of the constituents of the mixtures.

Thickening
Thickening is the process of removing excess water using gravimetric means. It is a cheap high
capacity process, which occurs in a tank made of steel or concrete, in which some concrete
structures with rakes or arms rotating within the suspension resulting in the formation of thick
slurry, which rests at the bottom ready for discharge. Thickeners may be batch or continuous
and are usually cylindrical in shape. The degree of thickening depends on the residence time
of particles and hence the thickener depth.

Thickener in operation

Thickener construction
Thickeners are made of steel, concrete or a combination of both. Steel is economical for sizes
of up to two metres in diameter. Concrete bases and tanks are more common for larger
thickeners. It is preferable to have a sloped bottom, since fine particles tend to slump and not
form a false bottom.

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Instrumentation for mechanism protection
A torque indicator should be installed on every drive, which reads the percentage maximum
continuous torque. As the indicator is installed on the drive head, it is normally equipped with
an alarm, which is activated at about 50% of the maximum torque. The alarm can either be
light or siren type. In addition, an auto-cut is usually installed to shut down the drive head,
when the torque reaches some predetermined value, normally with a maximum torque of
7090%.

Thickener components Tanks

These are usually cylindrical and are made of concrete or steel. The base slopes up to 4.5-8o,
80-140 mm though angles of up to 45o are known for larger units. The tank provides holding
time to produce settled solids and clarified liquor. The sloped bottom assists movement of the
concentrated solids toward the discharge point.

Feed well

The feed well

The feed wells usually carry 1m3/min and act as a buffer to energy from the stream and are
usually cylinders. They allow for flocculation by extending retention time. Mild agitation
occurs in the feed wells. The feed well function is to dissipate energy of movement in the feed
stream so as to cause the feed to enter the tank in a relatively quiescent condition and to provide
a means of introducing the slurry at an appropriate depth in the thickener.

Rakes
Rakes serve to deliver sludge to central discharge and help to increase pulp density. Rakes can
be arranged to rake 1-4 times/ revolution, but the most common method of arrangement is to
have two large rakes and two shorter ones, providing rakes in the central heavily loaded area.
The typical speeds are 5-8 meters/min.

The rake arms have three functions to fulfil in thickening, namely;

(i) move the settled solids towards the discharge point;
(ii) maintain a degree of fluidity in the thickener to ensure hydraulic removal and
(iii) increase underflow solids concentration by providing for channels for water to
escape from the thickening solids in the compression zone.

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The cone, Trench and Scrappers
These three perform an action similar to the rake arms so that underflow solids can be
discharged.

The Overflow launder

The launder collects clarified liquor for transport to the outlet. The best design practice is for a
uniform rate of overflow around the tank periphery.

The rake drive

The rake drive provides driving force (torque) to move the rake arms and blades against
resistance of the thickened solids.

The rake lift

The rake lift provides a means of lifting the arms out of contact with the more concentrated
solids so as to reduce the driving force demand from the rake drive. The lift will operate while
the rake arms are rotating.

Types of thickeners
Thickeners can be classified as conventional, high rate and paste thickeners.

i. Conventional thickeners
Can be categorised according to the rake driving mechanism i.e. centrally driven (e.g. bridge
type and column type) and peripherally driven (e.g. traction thickener).

Centrally driven
Bridge type
- Structure spans the tank

- Diameter < 45 m

- Central discharge cone

The bridge type thickener

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Column type
- Drive mechanism supported on stationery steel/concrete column connected to
drive mechanism

- Diameter < 180 m

- Circular trough

The column type thickener

Cable thickeners
- Hinged rake arm fastened to bottom of drive shaft

- Hinge gives simultaneous horizontal and vertical motion

- Cables pull rake arm

- Rake arm lifts automatically

Peripherally driven
- Diameter > 180 m
- Outer end of the arm has a carriage with motorized wheels
- Cannot lift
- Cannot be used for storage

Traction thickener

Traction thickener

ii. High rate thickeners

Differences compared to a conventional thickeners
 Deep feed well
 De-aeration of the feed
 Efficient horizontal feed distribution over entire thickener
 Controlled bed level
 Flocculant

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High rate thickener

iii. Paste thickeners

- Produce an ultra high density solids
- Longer residence time
- Rakes to dewater the sludge

Filtration
Filtration is the separation of solids from a suspension in a liquid by means of a porous medium
or screen which retains the solids and allows the liquid to pass. It is essentially a mechanical
operation and is less demanding in energy. Filtration serves to fulfil the following duties in
dewatering:
- To separate the solid material from the pulp in a dry form as possible without using heat
and

- To separate the liquid from the solid material. In this case, the liquid has the values such
as separating gold bearing liquid of pregnant solution from a cyanide pulp.

In operation a filter cake gradual builds up on the medium and the resistance of flow
progressively increases. During initial period of flow, particles are deposited in surface layers
of the cloth to form the true filtering medium. The rate of filtration depends on;
(i) the pressure drop from the feed to the far side of the filter medium. This is achieved
in pressure filters by applying a positive pressure at the feed and in vacuum filters
by applying a vacuum to the far side of the medium, the feed end being at
atmospheric pressure;

(ii) the area of filtering surface;

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 (iii) the viscosity of the filtrate;

(iv) the resistance of the filter cake and

(v) the resistance of the filter medium.

Slimes tend to “blind” the filter medium but flocculation reduces this and increases the voidage
between particles, making filtration easier.
The filter medium should be:
(i) able to retain solids without blinding;

(ii) mechanically strong;

(iii) corrosion resistant and

(iv) able to offer little resistance to the flow of filtrate as much as possible.

Classification of filters
Filters can be classified as pressure or vacuum filters.

Pressure filters
Pressure filters possess the following advantages over vacuum filters due to the virtual
incompressibility of solids;
 higher flow rates

 better washing and drying results

However, the continuous removal of solids from the pressure filter chamber can be extremely
difficult, thus the vast majority operate as batch filters. The most common pressure filters are
the plate and frame and the chamber press filters.

The plate and frame press

The plate and frame press consists of plates and frames arranged alternatively. The hollow
frame is separated from the plate by a filter cloth. A tight chamber is formed between each
pair of plates. A slurry is introduced to the empty frames of the press through a continuous
channel formed by holes in the corners of the plates and frames. The filtrate passes through the
cloth and runs down the grooved surfaces of the plates and is removed through a continuous
channel. The cake remains in the frame and when the frame is full, the filter cake can be
washed, after which the pressure is released and the plates and the frames separated one by
one.

The chamber plate

The chamber plate is similar to the plate and frame type except that the filter element consists
solely of the recessed filter. Individual chambers are formed between successive plates. All
chambers are connected by means of a large hole in the centre of each plate. This type of
process is common for treating slurries with a high solid content. They have an easier quick

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discharge method, produces a solid cake, which is easy to handle, and can produce a perfectly
clear water. It is simple. Versatile and has a low cost. Its disadvantages are that it is an
intermittent operation and has a high cloth wear rate.

Rotary vacuum filters

Rotary vacuum filters include the outside and inside drum filters, disc filters and the rotary belt
filters. The outside belt filter is the most common. Filtration is continuous. The filter medium
is a woven filter cloth.

The outside drum filter

The outside drum filter consists of a cylindrical drum, which rotates around a horizontal axis,
which may be a horizontal shaft, to which the drum is connected or a drum may be supported
on horizontal bearings. A rotary valve system regulates the filtration cycle. The valve system
consists of the parts, namely, the port plate, the valve seat and the wear plate. The valve seat
has as many holes on its periphery as there are vacuum pipes on the filter and each vacuum
pipe is connected to a pipe in the valve seat. The renewable wear plate is bolted through the
valve sear to the drum so that the wear plate and the wear seat rotate with the drum. The port
plate is stationery, it is held on the filter frame by an adjustable rod. A central pin or valve stem
on the valve seat holds the port tightly against the wear plate by means of a spring and a nut.
There is a channel along the periphery of the port plate connected to the filtrate or vacuum line
on the outside of which leads to the vacuum receiver.

The inside drum filter

The filter cake is formed inside the drum. The drum consists of two concentric shells with
vacuum or filtrate pipes between them. The filter cake is fastened to the inside surface of the
inner shell. The outer shell rests on rollers, which support and rotates the filter. The pulp to be
filtered is introduced on the filter. The end of the filter bearing, the rotary valve and the other
end is partial open for the removal of the filter cake either through a chute or for a longer filter
with a conveyor belt. It has the same cycle as the outside drum filter. Inside the drum is the
original the type but has been superceded by outside drum filter. It is now mainly used for
filtration of coarse particle, which are difficult to maintain in suspension.

The top feed filter

The top feed filter is used for filtration of very coarse material. The feed is introduced through
a feed tank, which distributes the pulp onto the top of the filter. Since the pulp is coarse, the
porosity of the cake is high and the rate of filter removal is high.

The belt filter

If the feed to a filter contains very fine slimes, the rate of filtration will be very low and this is
aggravated by the blinding of the filter cloth by the slimes- this cloth blinding also affects blow
offs. The result is a thin wet cake, which does not discharge well at the end of the cycle. The
portions of the cake that remains on the cloth are again submerged further deteriorating the
performance of the filter. To overcome some of these difficulties, belt filters have been
developed, in which the cloth leaves the drum at the end of the cycle and passes over a set of
rollers. The cloth with the cake on it is bent sharply over the discharge roller, which loosens
the cake and so assists in the cake discharge. After discharge, the cloth can be passed through
a wash trough, where it can washed from both sides. There are no blow offs in belt filter. In
another variance s, the belt is passed through of belt filter a pair of rollers, which squeezes out

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residual liquor. Its main application is in the chemical industry and filtration of fine flotation
concentrates.

Disc filters
Disc filters are continuous rotary vacuum filters, but instead of a drum filter on a hollow shaft,
they have a number of independent discs rotating on a hollow shaft. Each disc is composed of
a number filter leaves and each disc rotates in its compartment over the filter bowl. Vacuum is
applied through the hollow at, which also carries the filtrate away. Regulation of the cycle is
by means of a rotary valve. The number of discs per filter varies between two and twelve. The
advantage of this type of a filter is the considerable saving on floor space. The filter leaves,
which make up the disc can be

Sand filters
Sand filters are commonly used for the clarification of water. The resistance in such filters is
low. The driving force is gravity. Water percolates through large vessels with sand gravel.

Principles of filtration
The flow rate, dv/dt, of the filtrate through the cloth is given by dv/dt = kAΔp/lu,
Where, v is the volume k= constant (permeability) A=Cross-sectional area l=bed length
u=viscosity Δp= pressure drop for compressible cakes. For non-compressible cakes, dv/dt =
A2Δp/CvV.
Where Cv is a constant incorporating slurry pressure and porosity. Integrating, the slurry
filtration rate is given by t = CvV2/ A2Δp
i.e. The time for a specific volume is proportional to the square of the thickness. In filtration,
a balance must be made among immersion time, drying time, washing time, pressure drop and
product moisture. The most important factor is the pressure drop. A modified form of the
equation gives dv/dt = kAΔp/lu,

Other filtration parameters The

other filtration parameters are:
1. Filter Area- Capacity, which means the rate of solids deposition and the rate of filtration
which is the rate of liquid removal, is directly proportional to the surface area of the filter. 2.
Cake thickness- The rate of filtration is inversely proportional to the cake thickness. Therefore,
thinner cakes are drier than thicker cakes, all other things being equal, but the capacity is
directly proportional to the cake thickness.
3. Viscosity of filtrate- the rate of filtration is inversely proportional to the viscosity of the
filtrate. The viscosity can be decreased, thus increasing the filtration rate by raising the pulp
temperature or by use of low viscosity additives.
4. Pulp density- the rate of solids deposition is proportional to the solid concentration.
With material, which is easy to filtrate, it is beneficial to thicken the pulp, but for materials,
which is difficult to filter, e.g. very fine and clay pulp is usually filtered at a lower pulp density
in order to obtain the rate of filtration and so as to obtain dry cakes. Dilute pulps cannot be
filtered satisfactory on a continuous vacuum filter, because the dilute pulp will give inside
bridging, which results in blinding of the cloth before a cake of sufficient thickness can be
formed.
5. Particle size, shape and distribution- these have a great effect on the on the filtration
rate because the size and shape determine the specific surfaces of the particles in the cake and
also the porosity of the filter of the cake. The smaller the average particle size, and the lower

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the sphericity, the larger the specific surface and the larger the cake resistance. Cake resistance
is proportional to the square of the specific surface area. Fine and clay particles give high
resistance and, hence, lower size of the filtering rates. Size distribution, on the other hand,
affects porosity of the filter cake.
6. Flocculation- flocculation increases particle size and thus reduces the specific surface
and increase the porosity of the particles. Flocculated cakes have a much larger resistance and
reduce the rate of filtration. They are thick and are much wetter than unflocculated cakes.
7. Pressure drop- the rate of filtration is directly proportional to the difference in pressure
across the filter for incompressible cakes. For highly compressible cakes, however, it can be
shown that the rate filtration is independent of the change in pressure.
8. Depth of submergence- the greater the filter area in the pulp, the thicker is the cake.
However, the rate of solid deposition decreases rapidly after a short initial period. Little benefit
is obtained from a greater depth of submergence of the filter in the slurry. On the other hand,
the greater the depth of submergence, the less filter area for removal of the filtrate from the
cake and the wetter the cake will be. A thicker cake will also result in increased moisture
content.
9. Filter speed- the speed of rotation of a continuous vacuum filter is normally adjustable.
An increased speed means increased time available for solid deposition resulting in an
increased capacity, but this reduces the ability of the system to get rid of as much moisture as
possible. Thus it results in a wetter cake. Hence, high speeds are, therefore, preferred for
materials, which filter quickly. For materials, which do not filter easily, low speeds are
recommended.
10. Filter media- when choosing a filter medium, a decision must be made between a coarse
medium with low resistance giving high rates of filtration, but with less finer particles passing
through and a tightly woven cloth with high resistance, which will give maximum particle
retention. Since the loss of particles through the medium seizes as long as a cake of sufficient
thickness has been formed, preference is usually given to clothes of lower resistance, provided
that they do not blind. The durability of the filter cloth is also an important consideration. If a
cloth develops a small hole but is otherwise still capable of a good performance, such holes
can be patched up during operations.
Cloth blinding is caused by fine particles, which are in the pores or by chemical precipitation,
in particular, carbonates and sulphates. Blinding can sometimes be partially dealt with by
washing with dilute acids or by scrubbing to dissolve or loosen some of the blinding solids.
Tightly woven clothes are generally resistant to mechanical blinding. Many types of filter cloth
are on the market. Cloths woven from cotton dick are still the most popular, though synthetic
material is increasingly being used. Filters in leach plants require acid resistant cloths. In
selecting the type of cloth, the application is a critical importance even though the price might
be high.

5.0 SOLUTION PURIFICATION & ENRICHMENT

Introduction
- Leaching processes are rarely completely selective.
- Pregnant Leach solutions contain impurities and often purification prior to recovery of
the sought metal is done.

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Role of solution purification
- Removal of impurities.
- Upgrading or enrichment of solutions.
- To have a small volume of solution for subsequent processes. This would mean a saving
in energy and also less metal losses.

Techniques Employed
i. Solvent extraction/ liquid-liquid extraction ii.
Ion exchange utilizing solid resins
iii. Adsorption processes using activated carbon.

A. SOLVENT EXTRACTION
- Solvent extraction is also known as liquid-liquid extraction.
- In extractive metallurgy, solvent extraction consist of contacting an organic solvent
with an aqueous solution containing desired metal constituent.
- This is a separation process that takes advantage of the relative solubility of solutes in
immiscible solvents.
- The solute dissolves more readily and becomes concentrated in the solvent in which it
has a higher solubility.
- The process involves two main operations i.e. extraction and stripping.

i. Extraction
- Agitation of the aqueous phase with the organic solvent.
- The two immiscible solids are allowed to separate and the aqueous phase is
discarded or recycled.
- The process utilize the fact that the two phases are immiscible, therefore
after agitation the two will separate and the barren aqueous discarded or
recycled.

ii. Stripping
- The loaded organic phase is agitated with a small volume of suitable
solution and the stripped solvent is recycled.

Definition of terms
Extractant- this is the reagent/ solvent that is used to extract the valuable mineral or ions from
the feed, i.e it is the organic phase.
Extract- it is the loaded organic phase exiting after the extraction step containing the desired
product.
Barren solution- is solution containing very little or no valuable mineral ions
Raffinate- the exiting stream that has been depleted of the desired metal ions. This is the discard
solution.
Feed- Pregnant leach solution (PLS) i.e. the liquid containing the solute to be extracted in the
extraction process.

General scheme in Solvent Extraction

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 Leach

Extraction Stripping Precipitation

Barren
solution

loaded organic strip solution pure metal salt (to reduction) solution unloaded

organic phase recycle strip solution recycle Precipitating agent

Ideal extractants should fulfill the following

a. Good selectivity.
b. High extraction capacity.
c. Easily stripped.
d. Separate easily from water i.e. it should have;
i. appreciable difference in density.
ii. low viscosity.
iii. high surface tension.

e. Safe to handle i.e;

i. non-toxic.
ii. Non-flammable. iii.
Non-volatile.

f. Stable during storage or when in contact with acids or bases i.e. does not hydrolyze
during extraction or stripping.
g. Cheap and readily available.

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Extracting Reagents
Are classified into three broad groups;
a. Acidic- extract metals in cationic form.
b. Basic- extract metals in anionic form.
c. Neutral- extract metals such as solvent or addition compounds.

Acidic extracting agents

- Contains hydrogen atoms that can be ionized and replaced by metal cations e.g.
dialkaline phosphoric acid;
- 𝐷𝑖 − (2 ethyl hexyl) phosphoric acid ( 𝐷2EHPA)
2𝑅2𝐻𝑃𝑂4 + (2𝑎𝑞+ ) = 𝑀(𝑅2𝑃𝑂4)2 + 2𝐻(+𝑎𝑞)

𝑅𝑂 𝑂𝐻 𝑅𝑂 𝑂 𝑂 𝑂𝑅
2[ 𝑃 ]+ 𝑀2+ = 2𝐻+ + 𝑃 𝑀 𝑃
𝑅𝑂 𝑂 𝑅𝑂 𝑂 𝑂 𝑂𝑅

- Equilibrium exists between the metal ion complex and the metal ions.
- Low pH favours the metal ion, high pH favours the metal ion complex.
- Stripping is effected by introducing low pH system into the loaded phase.
- Other examples are the organic sulphonic acids or aliphatic mono carboxylic acid.

Basic extracting agents

- Extractants are primary, secondary, tertiary and quaternary amines.

- Basic extracting agents extract anions only hence metal ion to be extracted must exist
at least in partially ionic form.
- These unlike acidic agents, do not form covalent bonds with metal anion.
- The extracted compound is effectively an ionic salt consisting of the metal anion
complex and the organic cation e.g. extraction of uranium from a uranyl sulphate
solution using a tertiary amine extracting agent.
st
1 Step: The formation of onium ion. 2𝑅3𝑁 + 𝐻2𝑆𝑂4 ⇌ 2𝑅3𝑁𝐻+ + 𝑆𝑂42−

2nd Stage: In sulphuric acid the uranyl sulphate forms the sulphato complexes.
𝑈𝑂2𝑆𝑂4 + 2𝐻2𝑆𝑂4 ⇌ 𝑈𝑂2(𝑆𝑂4)43− + 4𝐻+

3rd Stage: The metal organic compound soluble in the organic phase is formed between the
onium ion and the uranium complex.

4𝑅3𝑁𝐻+ + 𝑈𝑂2(𝑆𝑂4)43− ⇌ (𝑅3𝑁𝐻)4𝑈𝑂2(𝑆𝑂4)3

In this case the effect of pH is not as simple as for the acidic agents since low pH favours
the formation of the onium ion but discourages formation of the uranyl complex. Hence
an optimum pH for metal extraction will depend on the equilibrium constant for the two
reactions.

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 Stripping
Stripping from basic reagents can be achieved using near neutral solutions or alkaline
solutions which convert the extracting agent to the free base form. Uranium can be stripped
in neutral solutions using a chloride salt solution. This stabilizes both the anion and the
cation (the organic soluble salt).

Neutral Extracting Agents

These are non-ionic. Metal extraction is effected by the transfer of complete metal salt into
the organic phase in the form of solutes or addition compounds. The extracting agents in
this compound in normally covalently bonded in the metal ion in the salt.

𝑈𝑂22+ + 2𝑁𝑂3− + 2(𝐵𝑈𝑂)3𝑃𝑂4 = 𝑈𝑂2(𝑁𝑂3)2(𝐵𝑈𝑂)3𝑃𝑂4

𝑇𝑟𝑖𝑏𝑢𝑡𝑦𝑙 𝑃ℎ𝑜𝑠𝑝ℎ𝑎𝑡𝑒

This reaction can be forced to the right by addition of 𝑁𝑎𝑁𝑂3 into the aqueous phase.
Stripping can be effected by having aqueous solution containing no 𝑁𝑂3.

Partition between Immiscible Liquids

- A solute will distribute itself between two immiscible solvents until at equilibrium
where the ratio of activities of the two liquids is constant at any given temperature.
- Thus for a solute dissolved in two immiscible solvents A and B which are in contact,
the free energy of solute in liquid A may be expressed as;

𝐺𝐴 = 𝐺𝐴𝑜 + 𝑅𝑇ℓ𝑛 𝑎𝐴 and in liquid B: 𝐺𝐵 = 𝐺𝐵𝑜 + 𝑅𝑇 ℓ𝑛 𝑎𝐵

- At equilibrium these two free energies of the solute;

𝐺𝐴 = 𝐺𝐵 thus 𝐺𝐴𝑜 − 𝐺𝐵𝑜 = 𝑅𝑇 ℓ𝑛 𝑎𝑎𝐵𝐴

ℓ𝑛 𝑎𝐵 = 𝐺𝐴𝑜−𝐺𝐵𝑜

𝑎𝐴 𝑅𝑇
but at a given temperature T, 𝐺𝐴𝑜 and 𝐺𝐵𝑜 are constant for a given solute in a particular
solvent hence;

ℓ𝑛 𝑎𝐵 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ⇛ 𝐵 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝑃° where 𝑃° is the partition

𝑎𝐴 𝑎𝐴 constant.

- Hydrometallurgical processes are concerned with total concentration of a particular

metal in each phase, thus a more meaningful expression becomes the distribution ratio
instead of 𝑃°.

𝑜𝑟𝑔
𝐷
𝑎𝑞 ∑[𝑀]

- This is the distribution coefficient which determine the ratio of solute concentration in
each solvent.

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 - When an organic solvent of volume Vo is equilibrated with an aqueous metal rich phase
of volume Vaq, fraction of metal extracted into the organic phase is given by;

𝐷
𝐹𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑒𝑥𝑡𝑟𝑎𝑐𝑡𝑒𝑑 (𝐸) = 𝑅 =

[ 𝐷 + (𝑉𝑉𝑜𝑟𝑔𝑎𝑞 ) ]

- This is the recovery factor, R, which is the fraction of the metal extracted into the
organic phase when a volume of the organic solvent is equilibrated with a volume of
the metal rich aqueous phase. - The phase ratio or the volume ratio (r) is given as; 𝑟
= 𝑉𝑜
𝑉𝑎𝑞

Initial moles of solute; [𝑀]𝑞′ 𝑉𝑎𝑞 𝑜𝑟 𝐶𝑎𝑞′𝑉𝑎𝑞

At equilibrium; 𝑛𝑜𝑟𝑔 = 𝑜𝑉𝑜 𝑛𝑎𝑞 = 𝐶𝑎𝑞𝑉𝑎𝑞

P = fraction in organic = 𝐶 𝑜𝑉 +𝑜 𝑉 𝐶𝑜𝑎𝑞𝑉𝑎𝑞 = 𝐷𝑟 𝐷𝑟 + 1 𝑜𝑟 𝐷 +𝐷

𝑉𝑎𝑞
𝑉𝑜

q = fraction in aqueous = 𝐶𝑎𝑞𝑉𝑎𝑞

𝐶𝑜𝑉𝑜 + 𝐶𝑎𝑞𝑉𝑎𝑞

1 1
= 𝑜𝑟
𝐷 + 1 𝐷 𝑉𝑉𝑎𝑞𝑜 + 1

+ 𝑞= 1

% = 100𝑃 = (1 − 𝑞)100

Problem; For a solution X determine the concentration and total amount in each phase if, Vo =
100ml, Vaq = 100ml and D = 3. Cx = 10-2M = feed concentration.

Multiple Extractants

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 S S S S

aq feed Raffinate

E1 E2 E3 E4

It is assumed that D for the stages remain constant.

Number of moles in each phase

Organic phase; 𝑝 𝑞𝑛−1𝐶𝑥′𝑉𝑎𝑞

Aqueous phase; 𝑞𝑛𝐶𝑥′𝑉𝑎𝑞

Solute concentration (Cn)

Organic; 𝑝 𝑞𝑛−1𝐶𝑥′ 𝑉 𝑉𝑎𝑞𝑜 𝑞𝑛𝐶𝑥′

′ 1 𝑛

Cn in terms of D, r and Cx; Aqueous: 𝐶 = 𝐶𝑥 {𝐷𝑟 + 1}

Total amounts extracted is the sum of all extracted.

(𝑝 + 𝑝𝑞 + 𝑝𝑞2 + … … … . + 𝑝𝑞𝑛−1)𝑥′𝑉𝑎𝑞 = (1 − 𝑞𝑛)𝐶𝑥′𝑉𝑎𝑞 𝑜𝑟 (1 − 𝑞𝑛) = 𝐸

1 𝑛

%𝐸 = 100(1 − 𝑞𝑛) = 100 [1 − ( )]

𝐷𝑟 + 1

Problem; How much would be extracted from;

a. Two sequential operations.
b. Ten 50ml sequential operations.
c. Comment on multiple contaction effect on metal extraction.
[Use previous example data]

Counter current extraction

Two phases pass continuously in opposite directions.

n 3 2 1
yn y3
y2 Xn-1 Xo y1 Vo
organic yn+1
Xn X2 X1
Vaq Aqueous

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Where; Vo- volume of organic phase Vaq-
volume of aqueous phase.
X- concentration in aqueous phase of extractable species. y-
concentration in organic phase of extractable species.

Mass balances
𝑉𝑎𝑞𝑋𝑜 + 𝑉𝒐𝑦𝒏+𝟏 = 𝑉𝒂𝒒𝑋𝒏 + 𝑉𝒐𝑦𝟏

𝑉0𝑦1 = 𝑉𝒂(𝑋𝒐 − 𝑋𝑛) + 𝑉𝒐𝑦𝒏+𝟏

𝑦𝟏 = 𝑉 𝑉𝑎𝑞𝑜 (𝑋𝒐 − 𝑋𝑛) + 𝑦𝒏+𝟏 (𝑠𝑡𝑎𝑖𝑔ℎ𝑡 𝑙𝑖𝑛𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛)

The line is the operating line for the McCabe-Thiele diagram. It is useful for establishing or
estimating the number of contacting stages in solvent extraction.

1 x

3
z

Conc of aqueous phase

- Abscisca for point x is solute concentration in the aqueous feed (X o) and the ordinate is
the solute concentration in extract (y1).
- Z- abscisca solute concentration in the raffinate and the ordinate is solute concentration
in the fresh organic feed yn+1 and is equal to zero for completely stripped or fresh
organic feed.
- Number of triangles gives number of contacting stages. Applies when information to
plot distribution isotherm is present.

Extraction Mechanisms
- In aqueous solutions, metals normally exist as ions or as aquo-cations e.g. Al3+ ions
exists as 𝐴(𝐻2𝑂)36+.
- The presence of solvating 𝐻2𝑂 molecules increases the similarity between the ionic
solvent and the solute.
- Most organic solvents are covalent in character, having low dielectric constants. Thus
to effect transfer, the metal species must change to a form compatible with the organic
solvent.

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 - The two requirements to bring this about are:
a. Charge neutralization.
b. Replacement of solvating 𝐻2𝑂 molecules by covalent type ligands.
- By this, metal species will become closer in type to the organic solvent in which it is
likely to dissolve at the same time reducing its solubility in aqueous phase. The change
can be achieved in one of the following.

a) Formation of uncharged co-ordination compounds

- Co-ordination compounds are formed between complexing agents which have excess
electron pairs, and metal ions with electron pair deficiencies.
- Transition elements because of their unfilled lower orbitals, are susceptible to complex
formation.
- Many co-ordination complexes are complex ions that are not extracted but some are
neutral and may be readily extracted into an organic phase (e.g. 𝐺𝑒𝐶𝑙4into 𝐶𝐶𝑙4).
- Chelates are the most important co-ordinate compounds group in solvent extraction.
- Chelating agents are reagents having at least 2 ligand atoms in the molecule and thus
give rise to ring formation.
- Uncharged chelates possessing 5 or 6 membered rings are most stable, very soluble in
non-polar solvents and insoluble in aqueous phase.
- Chelation example is reaction of 𝐴𝑙 ions with 8-hydroxyquinoline. This gives a complex
which is soluble in chloroform.

b) Ion Exchange Processes

i. Cation exchange processes.
- Involves the exchange of metal cations with the hydrogen ions of the reagent dissolved
in the organic phase.
- These extractants may be termed liquid cation exchangers and include organic acids
e.g alkyl phosphoric acids and carboxylic acids.
- 𝑍𝑛 may be extracted with versatic acid;
2𝑅1𝑅2𝐶𝐻3 𝐶𝑂𝐶𝑂𝑂𝐻 + 𝑍𝑛2+ = (𝑅1𝑅2𝐶𝐻3𝐶𝐶𝑂𝑂)2𝑍𝑛 + 2𝐻+

ii. Anion Exchange Process

- Involve exchange of complex metal anions with anions of long-chain alkyl amines.
- These include all classes of amines from primary to tertiary and quaternary ammonium
types.
- Extractants often referred to as liquid anion exchangers. For example, tertiary amine
tri-octlyl amine (R3N) can be used to extract platinum from acid chloride solutions;

𝑅3𝑁 + 𝐻𝐶 = 𝑅3𝑁𝐻𝐶𝑙 𝑎𝑛𝑑 2𝑅3𝑁𝐻𝐶𝑙 + 𝑃𝑡𝐶𝑙62− = (𝑅3𝑁𝐻)2𝑃𝑡𝐶𝑙6 + 2𝐶𝑙−

c) Solvation with ion association

- Solvation: replacement of solvating water molecules of an aquo-cation by organic
solvent molecules. Extractants of this type include; ethers, esters and ketones.
- Charge neutralization is achieved by association with an ion of opposite charge. For
example diethyl ether extraction of iron from chloride solution.
- High chloride concentration usually in form of HCl, brings about anion formation;

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 𝐹(𝐻2𝑂)63+ + 4𝐶𝑙− = 𝐹𝑒(𝐻2𝑂)2𝐶𝑙4− + 4𝐻2𝑂

- This is followed by salvation with diethyl ether molecules to yield; Fe[( C 2H5)2O]2Cl4-
- Diethyl ether molecules may become protonated by reaction with oxonium ions;
(𝐶2𝐻5)2𝑂 + 𝐻3+𝑂 = (𝐶2𝐻5)2𝑂𝐻+ + 𝐻2𝑂 and electrostatic attraction between the
two types of ions results in the formation of an ion-association compound;
{(C2H5)2OH+.Fe[(C2H5)2O]2Cl4-}.
- Thus dehydration and charge neutralization are achieved favouring transfer to the
organic phase.

B. ION EXCHANGE PROCESSES

- Ion exchange is a reversible process in which a dissolved ion species is taken up by a
solid in a stoichiometric manner.
- There is reversible interchange of ions between an insoluble solid phase (ion exchanger)
and a solution phase.
- It is a reversible chemical reaction where an ion from solution is exchanged for similarly
charged ion attached to an immobile solid particle.
- Ion exchangers can be naturally occurring (inorganic) or synthetic which are based on
the condensation polymerization of phenols with formaldehyde.
- Sulphonation with H2SO4 acid introduces a strong acid function group –SO3H.
- Other acid groups are the carboxylic group –COOH, phosphoric acid group and arsenic
acid group.
- All the acid inorganic groups produce cation exchange resin.
- Anion exchange resins can be produced similarly by basic functional groups. These are
usually substituted ammonium groups.

Process chemistry
M-A+ + B+ = M-B+ + A+ cationic exchange system
M+C- + D- = M+D- + C- anionic exchange system

Ion exchange steps include;

a) Sorption- passing the solution containing the valuable mineral through a resin bed/ resin
column containing the ion exchange.
- The value metal ions transfer from the aqueous phase to the organic phase i.e. the resin
phase.
- Bed or resin saturation is detected by the appearance of the value metal in the effluent,
pumping must then be stopped.
- The process is operated on a batch scale.

b) Elution- washing of the resin (saturated) with suitable aqueous solution.

Feed (leach solution) water

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 Resin bed

Sorption washing

Effluent
loosely adsorbed effluent

Eluant water

washing

Resin bed

Elution

Eluate (pregnant solution) Waste

- Ion exchange is carried out under equilibrium conditions. A given solution volume is
shaken with weight of resin, till equilibrium is reached.
- In this case uptake of value metal species on the resins is characterized by the
distribution factor, D.
- Where D = 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑝𝑒𝑟 𝑔𝑟𝑎𝑚3 𝑜𝑓 𝑟𝑒𝑠𝑖𝑛
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑝𝑒𝑟 𝑐𝑚 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

- The higher the value of D, the greater the affinity of resin for metal ion than its solubility
in aqueous form.

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Ion exchanger
- Ion exchangers are solid material which are able to sorb negative or positive charged
ions from an electrolyte solution and release an equivalent amount of other ions of equal
charge sign to the solution.
- The exchanger is a framework or matrix which carries a positive or negative charge
compensated by counter ions of opposite charge.
- Counter ions have the same charge as those on the value metal.
- Counter ions are mobile and replaceable.
- Positively charged matrix- anion-exchanger and negatively charged matrix-
cationexchanger.

Sponge Model of the Ion Exchanger

- The model compares the ion exchangers to a sponge with counter ions floating in pores.
- The sponge immersion in a solution releases the counter ions into solution to preserve
or for charge balance in the sponge.
- A stoichiometric number of ions from the solution occupies the pores.

Typical reactions
R-Y+ + B+ = R-B+ + Y+ cationic
Y+resin + B+aq = B+resin + Y+aq

R+X- + A- = R+A- + X- anionic

X-resin + A-aq = A-resin + X-aq
Classification or types of ion exchange resins
1. Strong acid cation exchange resin
- They are so named because their chemical behavior is similar to that of a strong acid.
- The resins are highly ionized in both acid and the salt form e.g R-SO3H and R-SO3Na.
- They ionize in the whole pH range i.e 0 – 14.
- Regeneration requires a strong acid e.g. purification of water/ deionization of water
were replacement of Ca2+ amd Mg2+ ions with Na ions occurs.

2. Weak acid cation resin

- Functional group is –COOH, carboxylic group.
- These resins behave similarly to weak organic acids that are weakly dissociated.
- At a pH less than 6, there is negligible ionization energy capacity hence a decrease in
exchange capacity.

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 Weak acid

Weak base

3 4 5 6 7 8 9 10 11

- Regeneration requires a weak acid because of the affinity of H+ ions.

- Degree of dissociation of a weak resin is strongly influenced by solution pH.

3. Strong base anion resin

- Functional group is is quaternary ammonium groups e.g. –N(CH3)3OH.
- Like strong acid resin, strong base resin are also highly ionized in the whole pH range.
- Not affected by changes in pH.
- These resins can be used in the hydroxide for example in water deionization. - For
regeneration they require strong bases like NaOH.

4. Weak base anion resin

- These resins are like weak acid resins in that the degree of ionization is strongly
influenced by pH.
- The exchange capacity decreases with an increase in pH.
- Functional group is alkaline ammonium species.
- Regeneration requires a weak base like ammonium hydroxide.
- The weak base resins can be used to sorb strong acid. In waste water treatment, strong
acid resin used to remove ions and then a weak base resin is used to neutralize the strong
acid.

Characteristics of ion exchange resins (IER)

- Main properties that govern the resin performance are; 1.
Selectivity coefficient.
2. Separation factor.
3. Ion exchange isotherm.
4. Ion exchange capacity.
5. Break through capacity.

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Selectivity
- There are physical and chemical reasons why ion exchangers preferably attract ions from
solution in place of its counter ions.

Selectivity coefficient
- Measures the ability of the resin to selectively adsorb a certain metal ion in preference
to another.
- It is the thermodynamic equilibrium constant for an ion exchange reaction of the type;
A+ + BR = B+ + AR

𝐴 [𝐴𝑅][𝐵+]

→ 𝐾𝐵 =

- The coefficient defines two characteristics of the resin.

a. Exchange of equivalent amounts of ions (meaning counter ions and value counter ions).
b. Preferential intake of an ion over another.

- gives ratio of A+ and B+ in the resin phase which is in equilibrium with aqueous
concentration of A+ and concentration of B+.
- For K = 1, resin has no preference for A+ or B+.
- Easy separation achieved for K values >>1, but this can lead to problems in elution and
regeneration.
- Therefore K must be determined for each particular operation.

Factors affected by K
1. Flow rate.
2. Choice of eluant.
3. Degree of separation.

Separation factor(α)
- Ion exchangers metal affinity can be expressed by distribution coefficient, d.
d = 𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑝𝑒𝑟 𝑔𝑟𝑎𝑚3 𝑜𝑓 𝑟𝑒𝑠𝑖𝑛

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑝𝑒𝑟 𝑐𝑚 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

- Comparing the distribution ratio of two ions gives the separation factor (α). - α =
𝑑𝐴 where dA is distribution coefficient of metal ion A and dB for metal ion B.
𝑑𝐵
- Parameter analogous to the selectivity coefficient in that it determines the selection of
one metal over the other.
Ion exchange isotherm

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 - If we plot the equivalent ionic fraction in solution (XA) against equivalent ionic fraction
of the same ion in the resin phase (YA); Curve 1
- It shows favorable equilibrium for the adsorption of B on the resin in preference to A.

Curve3
- Represents the reverse of one.

Curve2
- Resin shows no preference of either species.

NB: Ion exchange isotherm is the most useful way of expressing equilibrium behavior in ion
exchange.

Breakthrough Capacity (B.T.C)

- B.T.C obtained from the breakthrough curves as shown below.
- Breakthrough Capacity (B.T.C) is defined as the quantity of ions that can be taken up
by a resin column under given conditions before leakage occurs into the effluent.
- Determined from breakthrough curves which is C/Co against volume of influent passing
through the column or against the quantity of metal ions contained.
- B.T.C is defined by the point X where the ratio C/Co becomes finite.

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 x

Where; A - C depict decreasing flow rate.

Co – influent concentration.
C- effluent concentration.

Effect of flow rate

- Low flow rate results in steeper curves and high B.T.C value.
- At infinitely slow flow rate breakthrough capacity is equal to total capacity.
- Point of inflexion of the curve denotes the resin total capacity.
- B.T.C always < total capacity and affected also by, resin size, column dimensions and
temperature.

Elution or Regeneration
- Adsorbed ions are displaced from the resin by passing an excess electrolyte termed eluant
or regenerant through the resin column.

Elution curve

Volume of eluate

- Eluting agents include; acid, bases and complexing agents.

- To recover metal from a cation resin column, a 2M acid can be used. - For a
bivalent metal; R2M + 2H+ = 2RH + M2+

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 - Selective elution can be done using a complexing agent.
- Resin regeneration is partially carried out only to an economic limit.
- Continuous ion exchange techniques or multiple fixed bed units in series can give
increased regeneration efficiencies.
- When reaction takes place like neutralization of the resin in the acid with base as
regenerant, stoichiometric amount of chemicals are used.

Systems application of Ion Exchange Resins

1. Water treatment (water demineralization).
2. Recovery of metal ions from industrial waste solution.
3. Rare earth metals separations
4. Removing unwanted, toxic or dangerous constituents.

Strong acid resins application

- Used extensively in water and waste solution treatment and in demineralization.
- Have excellent selectivity for the polyvalent ions over mono-valent ions.
- Effective over a wide pH range (0-14).
- Regenerated with brine or 10% HCl or 1 – 8% H2SO4 acid.
- They have a low affinity for Na+ and H+ thus up to 200 – 300% excess eluant.
- Marketing names are; Dowex 50, Dowex 50w, Amberlite 1R120, Duolite C20,
Permutite.
- Supplied in -20 to +50 mesh.
- Density arount 1.3g/cm3.

Weak acid resins application

- Carboxylic group COOH is most common.
- Effective pH range 4-14.
- High total capacity at pH > 7.
- Generated easily with stoichiometric quantities of base.
- Very effective for bi-carbonate salts removal, Cu(NH3)42+ is readily adsorbed on the
resin and recovered with a weak acid.
- Available trade names; amberlite 1RA425, Dowex 1, permutite 51C.
- Basic or neutral solution complexes like uranium carbonate adsorbs significantly.
- Also, cyanide complexes of Au, Ag, Cu, Ni, Cd and Zn can adsorb significantly.
- Selective elution techniques are required for the recovery and separation of CN-
complexes.

Weak base resins application

- Ionized in the salt form and thus effective at pH less than 7.
- Can also be used in water purification and demineralization.
Tertiary ammine resins used in the recovery of U3O8

Case studies
Connemara Gold mine (Zimbabwe)
Langer Henrich uranium (Namibia)
Metsep (South Africa)

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Practical Applications of Ion Exchange Processes
Ion Exchange of Uranium
- Sulphato complexes formed by uranium in H2SO4;
UO22+ + SO42- = UO2SO4 K = 50
2- 2-
UO2SO4 + SO4 = UO2(SO4)2 K = 350
2- 2- 4-
UO2(SO4)2 + SO4 = UO2(SO4)3 K = 2500

- Trisulphato complex is the most stable.

- Maximum sorption at H2SO4 concentration of 10-2M.
4RCH2N(CH3)3X + UO2(SO4)34- = [RCH2N(CH3)3]4UO2(SO4)3 + 4X- -
The distribution coefficient is > 10 000.
- Competitive sorption by impurities for example Mn, Cu, Mg and Fe(II) is negligible.
- Fe(III) often present as Fe(OH)(SO4)22- which shows significant affinity 𝛼𝐹𝑒𝑈 > 1000.
- Serious competitive sorption arises from Ti, Cr, Mo, V, Zr anionic species.
- Sorption of these species are irreversible to some extent and thus give rise to resin
poisoning.
- In Carbonate – Bicarbonate leach systems you have;
UO3 + CO32- + HCO3- = UO2(CO3)34- + H2O (Leaching)
4RCH2N(CH3)3X + UO2(CO3)34- = [RCH2N(CH3)3]4UO2(CO3)3 + 4X-

Separation of U and Fe(III) species

1.0

𝐶
𝐶𝑜
0.5

Fe(iii) B.T U(iv) B.T

Volume of effluent

- The graphs show sorption B.T.C for U (iv) contaminated with Fe(iv).
- Spit eluate technique used where the first volume containing the unwanted ions (Fe(iii))
is collected and then the final volume would contain the target metal ions.
- Metal recovery by ion exchange treatment of waste water and effluents for the purpose
of recovering metal values, removal of unwanted toxic or dangerous constituencies
results in purified water.

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Resin Poisoning
- Anion exchange resin is reasonably specific for uranium take up.
- Sorptions of other ions occur and some of these are not completely removed during
elution (irreversible sorption).
- These are regarded as resin poisoning, they reduce resin capacity.
- Poison takes up an increasing proportion of the exchange sites of each cycle, e.g.
solution containing 300mg/L uranium and 10mg/L Mo, resin capacity decrease to 60%
after 20 cycles.

Operational Techniques
1. Batch method.
2. Column method( i. Fixed bed and ii. moving bed).
3. Fluid bed method.

1. Batch Method
- This is the simplest but also most inefficient method.
- The resin and solution are mixed until equilibrium is attained.
- There is use of filtration method to separate the eluate and the gangue.
- The method is useful when;  The equilibrium is favourable.
 The reaction goes to completion.

2. Column Method
a. Fixed Bed Resin
- Is the most widely used method, either downward or upward solution flow through the
bed.

Fresh solution

Barren solution

- Column is considered as a large number of batch operations in series.

- Can be used in series or as a single unit.
- For a single unit the column is run to break even.
- Series operation, is a possibility of fully utilizing the resin total capacity.
- Saturation occurs at a head/ lead column before breakthrough occurs in the tail column.

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 b. Moving Bed (Counter – Flow System)
- These are single column systems where complex regeneration is not necessary, a
downward flow adsorption and up flow elution technique provides high adsorption
efficiency and low chemical costs. - Methods using this technique include;  Packed Bed.
 Buried Collector.
 Pressed Bed.

Saturated resin direction of solution flow influent

column

solution resin particles

effluent (barren solution)

fresh resin

direction of resin flow

- Methods are primarily used for water treatment.

- Application in Hydrometallurgy limited to waste solution and metal recovery.

Advantages
- The whole column is active.
- Less resin consumption.
- Smaller sized equipment.
- Low or less chemicals consumption.

3. Fluid Bed Continuous System

- There is a series of Batch Ion Exchange vessels.
- Resin and solution agitated together until equilibrium, contacting continuously until the
solution is barren.
- Resin can also be moved counter – currently, i.e. for truly continuous systems.

Advantages
- Fluidized bed means no problems presented by dirty or slimes; this is the basis for resin
in pulp which is used extensively in uranium processing.
- Resin in pulp is adapted for the treatment of ores where filtration or clarification gives
problems. Hence considerable savings in capital cost on filters and thickeners.

6.0 PRECIPITATION

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- Precipitation is the formation from solution of a solid product as the result of dilution or of
addition of a reagent to the solution.
- Selective precipitation can be achieved by pH control.
- Objective is separation and/recovery of metals.
There are two forms: -

i. Chemical precipitation
ii. Reductive precipitation

• Precipitate should possess the following properties;

- Should be coarse
- Dense
- Filterable (filtration to separate)
- Easily washed and handled

Chemical Precipitation
Does not involve electrons. Examples include;
a) 𝑃𝑡𝐶𝑙62− + 2𝑁𝐻4+ = (𝑁𝐻4)2𝑃𝑡𝐶𝑙6

b) 𝐹𝑒3+ + 3𝑂𝐻− = 𝐹(𝑂𝐻)3 (hydrolysis of ferric ions).

Thermodynamic considerations
For a sparingly soluble salt MmPn

𝑀𝑚𝑃𝑛 = 𝑚𝑀𝑍+ + 𝑛𝑃𝑦− at equilibrium, 𝐾𝑠𝑝 = [𝑀𝑍+][𝑃𝑦−]𝑛

→ Metal ions in solution after precipitation;

[𝑀
𝑧+]𝑚 = [𝑃𝐾𝑠𝑝𝑦−]𝑛

Precipitation of metal sulphides

Can be done using hydrogen sulphide (H2S) gas. H2S dissolves in water and is a weak dibasic
acid which dissociates as: -

𝑎
𝐻2𝑆 = 𝐻+ + 𝐻𝑆− 𝐾1 = 𝐻𝑆−𝑎𝐻+

𝑎𝐻2𝑆

𝐻𝑆− = 𝐻+ + 𝑆2− 𝐾2 = 𝑎𝐻𝑎+𝐻𝑎𝑆𝑆−2−

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 𝑀2+ + 𝑆2− = 𝑀𝑆

[𝐻+]2[𝑆2−] −21

At 298𝐾, 𝐾1𝐾2 = [𝐻2𝑆−]= 1.69 × 10

[𝑆2−] = 1 .5[ ×10+]2−22 𝑝𝐻 = − log[𝐻+]

log[𝑆2−] = log 1.5 × 10−22 + 2𝑝𝐻

∴ [𝑆2−] is a function of pH, 𝑃𝐻2 and temperature but pH has the greatest effect.

- Selective precipitation is achieved by appropriate adjustment of pH.

- Higher temperatures and pressure offer higher rates of precipitation.

pH [𝑆2−] 𝑀
-2 1.5 × 10−26
0 1.5 × 10−22
2 1.5 × 10−18
4 1.5 × 10−14
6 1.5 × 10−10
8 1.5 × 10−6
10 1.5 × 10−2

- This data if applied to Ksp values, one can determine pH above which precipitation of a
particular MS is thermodynamically feasible.
- On the other hand at a given pH the thermodynamic tendency of precipitation formation
can be deduced. For example at pH 2 and 25ºC, [S2-] = 1.5x10-18M.
- A solution with 10−2𝑀 of each of 𝑀𝑛2+ 𝑎𝑛𝑑 𝐶𝑢2+;

→ [𝑀𝑛2+][𝑆2−] = 10−2 × 1.5 × 10−18

= 1.5 × 10−20

𝐾𝑠(𝐶𝑢𝑆) = 7.94 × 10−37

𝐾𝑠(𝑀𝑛𝑠) = 3.16 × 10−11

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- Thermodynamically 𝐶𝑢𝑆 can precipitate but MnS cannot. Hence 𝐶𝑢2+ ions are separated
from 𝑀𝑛2+, filtration done to separate the precipitate and solution. - Overall
precipitation reaction;

𝑀2+ + 𝐻2𝑆 = 𝑀𝑆 + 2𝐻+

Sherritt-Gordon Ammonia Leach Process

- Process is used for the separation of base metals.
- Treatment of Ni rich concentrates makes use of 𝐻2𝑆 to completely remove 𝐶𝑢 from leach
solutions.
- Later, after reductive precipitation of most of the 𝑁𝑖 by hydrogen gas, 𝐶𝑜 𝑎𝑛𝑑 𝑁𝑖 remaining
are extracted from solution as sulphides.
- The flow diagram is given below.

Ni – Rich concentrate
NH3
Air
Air
Secondary Leach Primary NH3 pressure Leach
Solution

Cu Boil Cu(II)Sulphide

Solution

Cu Strip Cu/ Ni Sulphides (to 1º Leach)

Solution

Oxyhydrolysis
45 – 50g/L Ni

Ni Pressure Reduction Ni powder

Co/ Ni Strip Co/Ni Sulphides to Co plant

Residue

Residue

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 H2S

Air

H2

H2S (autoclaves)

NH4SO4 Recovery

Precipitation of Metal Hydroxides:

- Sparing soluble hydroxides can be formed by hydrolysis of metal ions;

𝑀𝑧+ + 𝑛𝐻2𝑂 = (𝑂𝐻)𝑛 + 𝑛𝐻+

- Hydroxides also dissociates in water as;

𝑀(𝑂𝐻)𝑛 = 𝑀𝑧+ + 𝑛𝑂𝐻−

𝐾𝑠𝑝 = 𝑎𝑀𝑧+ × 𝑎𝑂𝐻−𝑛

- Thermodynamic tendency of precipitation can be determined using 𝐾𝑠𝑝 values of metal

ion concentration. pH above which hydrolysis occurs can be determined.

Example:
A solution of 𝐶(𝐼𝐼𝐼) ions with an activity of 10−6𝑀, 𝐾𝑠𝑝 (𝐶𝑜(𝑂𝐻)3) = 3.16 × 10−45

Answer:
𝐶(𝑂𝐻)3 = 𝐶𝑜3+ + 3𝑂𝐻− at 25ºC 𝐾𝑠𝑝 = 𝑎𝐶𝑜3+. 𝑎𝑂𝐻3 − = 3.16 × 10−45

∴ 𝑎𝑂𝐻3 −
 Hence 𝑝𝑂𝐻 = 12.8 or 𝑝𝐻 = 1.2
 Above a 𝑝𝐻 𝑜𝑓 1.2 hydrolysis of Co(III) ions occur forming a precipitate of
𝐶(𝑂𝐻)3.

- If 𝑎𝐶𝑜3+ is increased equilibrium pH decreases, hence precipitation favorable.

- Strong alkali reagents e.g. 𝑁𝑎𝑂𝐻 not suitable as precipitation agents for (𝑂𝐻).
- pH control important in precipitation, can be achieved by the use of buffers or suitable
metal oxide, hydroxide or carbonate.

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Separation of 𝑭𝒆
- 𝐹𝑒 often an impurity in leach solutions.
- Mainly present as 𝐹𝑒3+or 𝐹𝑒2+.
- Hydrolysis of 𝐹𝑒3+favorable under acidic conditions ≈ 𝑝𝐻 3 𝑎𝑛𝑑 𝐹𝑒2+ 𝑝𝐻 8.
- Selective hydrolysis of certain metals can be done, in acidic conditions, in the presence of
𝐹𝑒2+.
- 𝐹𝑒3+can be precipitated in the presence of other metal ions.
- In 𝑁𝑖 extraction, 𝐹𝑒 is oxidized to 𝐹𝑒3+ and 𝑁𝑖 (𝑂𝐻)2 is the hydrolyzing agent. Reaction
is;

2𝐹𝑒3+ + 3𝑁𝑖 (𝑂𝐻)2 = 2𝐹𝑒(𝑂𝐻)3 + 3𝑁𝑖2+

- 𝑁𝑖 (𝑂𝐻)2 has the advantage of not introducing foreign ions since Ni2+ already present.

Jarosite Process
- Used when high concentrations of 𝐹𝑒 present e.g. in roasted zinc concentrates
(often 𝑍𝑛𝑂. 𝐹𝑒2𝑂3).
- Jarosite is a mineral 𝐾𝐹𝑒3(𝑂𝐻)6(𝑆𝑂4)2
- Potassium (K) can be substituted by 𝑁𝑎+, 𝑁𝐻4+, 𝑅𝑏+, 𝐻3+ e.t.c.
- Precipitation at 95°C, pH 1.5, the precipitate is crystalline and easily separated with little
losses of zinc.

ZnOxide Calcine Spent electrolyte

Neutral Solution
Neutral Leach Cementation E/W Cathode Zinc
Purification (Zn)
Residue
Spent electrolyte
H2SO4
Hot Acid Leach
Residue (Pb/ Ag) to smelter
Solution

NH3 Jarosite Precipitation

& Calcine
Jarosite (plus residue)

- Zinc Oxide calcine leached with solution from Jarosite separation made up with spent
electrolyte (25%).
- 𝑍𝑛𝑂 dissolves but the excess hydrolyse 𝐹𝑒3+ in solution.
- Co-precipitation of impurities (𝐴𝑠, 𝑆𝑏, 𝑆𝑛 & 𝐺𝑒) occurs.
- Solution further purified by Zn cementation before electrowinning.
- Residue from neutral leach stage which contains 𝑍𝑛𝑂. 𝐹𝑒2𝑂3 and excess 𝑍𝑛𝑂 is leached at
95ºC with 𝐻2𝑆𝑂4.

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- 𝑍𝑛 dissolution occurs and residue is mainly lead or silver.
- 𝑍𝑛 pregnant solution goes for jarosite precipitation.
- The acid is neutralized by addition of calcine and the precipitation temperature = 95°𝐶
effected by 𝑁𝐻3.
- 𝐹𝑒 (small amount) is left in solution so as to achieve co-precipitation of impurities in the
neutral leaching stage.

• Other pH – dependent precipitation systems exist e.g. carbonates, selenides, arsenates and
phosphates.

Reductive Precipitation
- Process essentially electrochemical in nature.
- Thermodynamic data can be used to compute potential of metal to be reduced from
solution and to choose suitable reducing agent.

Two forms of reductive precipitation i.

Using a metal (cementation).
ii. Using a gas.

i. Cementation
- Is the reductive precipitation of a metal from solution using another metal as the
precipitant.
- For example; 𝐶𝑢 can be extracted from solution using 𝐹𝑒.
𝐹𝑒 + 𝐶𝑢2+ = 𝐹𝑒2+ + 𝐶𝑢 𝐸𝜃 = 0.777𝑉

𝑎𝐶𝑢2+
ratio high at the beginning but would fall as reaction proceeds and potential also
𝑎𝐹𝑒2+
reduces.

Question:
How much 𝐹𝑒 is required to precipitate 1 tonne of 𝐶𝑢?

Merrill-Crowe Process
𝐴(𝐶𝑁)−2 + 𝑒 = 𝐴𝑢 + 2𝐶𝑁− 𝐸𝜃 = −0.67

𝑍(𝐶𝑁)24− + 2𝑒− = 𝑍𝑛 + 4𝐶𝑁− 𝐸𝜃 = −1.26

−+ 𝑍𝑛 = 2𝐴𝑢 + 𝑍(𝐶𝑁)24− 𝐸𝜃 = 0.59𝑉 2𝐴𝑢(𝐶𝑁)2

See gold hydrometallurgy for notes.

Other examples;
In the electrowinning of 𝑁𝑖, 𝐶𝑢2+ may be removed from 𝑁𝑖 anolyte solutions by
cementation with 𝑁𝑖 powder.
𝐶𝑢2+ + 𝑁𝑖 = 𝐶𝑢 + 𝑁𝑖2+

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ii) Gaseous Reduction
- Can be effected by; 𝐻2, 𝐶𝑂, 𝑆𝑂2 etc.

Hydrogen gas
𝑍𝐻+ + 𝑍𝑒− = (𝑍 2 ) 𝐻 2

𝑀𝑍+ + 𝑍𝑒 = 𝑀

𝑀𝑧+ + (𝑍 +

2)2 = 𝑀 + 𝑍𝐻

Application of Nernst equation:

𝐶𝑜2+ + 𝐻2(𝑔) = 𝐶𝑜 + 2𝐻+

𝐸=𝐸
° + 𝑅𝑇2𝐹 𝐼𝑛 {𝑎𝑎𝐻2𝐻 } 𝐸° = 0 𝑝𝐻 = −𝑙𝑜𝑔𝑎𝐻+
+2

𝑅𝑇 𝑅𝑇
⇛ 𝐸 = −2.303 − 2𝐹 ℓ𝑛 𝑎𝐻2 (𝑖)

- Potential of the hydrogen system is a function of pH and activity of hydrogen gas.

- 𝑎𝐻2is proportional to partial pressure over a range at 298K.

𝐸 = −0.0591𝑝𝐻 − 0.0296 𝑙𝑜𝑔 𝑃𝐻2 (𝑖𝑖) -

Higher pH gives a more negative potential.
- Consider 𝑁𝑖2+⁄𝑁𝑖 system.
𝑁𝑖2+ + 2𝑒− = 𝑁𝑖

- If [𝑁𝑖2+] = 10−4𝑀 Nernst equation gives at 298K; 𝐸 = −0.25 + 0 . log 10−4 =

−0.368𝑉

- Substituting E into (ii) and taking 𝑃𝐻2 = 1𝑎𝑡𝑚

⇛ 𝑝𝐻 = 6.2 (equilibrium pH).

- Above pH 6.2 precipitation of Ni thermodynamically feasible. Equilibrium pH can be

obtained from a modified 𝐸 − 𝑝𝐻 diagram.
- The digram is illustrated below for the Nickel system.

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0.1

0.0
Activity Ni2+ = 100
Activity = 10-2
= 10-4

𝑎𝑁𝑖 2+ =10−4
- H2 = 1 atmos
0.2

-
0.3

-0.4

-0.5
-0.6

-0.7
0 3 5 7 9 11 13 15
pH

- 𝐸⁄log 𝑎𝑀𝑧+put onto 𝐸⁄𝑝𝐻 curves for 𝐻2 system for a number of metals produce a
hydrogen precipitation diagram.
- Reduction depends on relatively severe temperatures and pressure conditions and on
control metal ion continued and pH.
- Additional of microscopic crystallites to serve as nuclei of powder particles can be done
if necessary.
- Hydrolysis can disturb reduction of metal ions.

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 𝑀2+ + 2𝐻2𝑂 = 2(𝑂𝐻)2 + 2𝐻+

- (𝑂𝐻)2 = 𝑀2+ + 2𝑂𝐻− this dissociation would control reduction rate.

- Hydrolysis minimized if metal ions present as complex compounds.

- For example 𝑁𝐻3 leaching of 𝐶𝑢, 𝑁𝑖 and 𝐶𝑜 ores, ammine complexes formed e.g.
[𝐶(𝑁𝐻3)4]2+ stable and no hydrolysis.

𝑼𝑶𝟐 Precipitation
- 𝐸 − 𝑝𝐻 diagram of specific metal −𝐻2𝑂 system used.
- For uranium, 𝐸 − 𝑝𝐻 diagram shows 𝐻2 line being more negative in potential than
𝑈𝑂22+ + 2𝑒− = 𝑈𝑂2 equilibrium from 0 − 14 𝑝𝐻.
- For hydrolysis (precipitation) the pH should not fall below 2 because 𝑈4+ soluble
species formation depicted.
- Precipitation is 𝑈𝑂22+ + 𝐻2 = 𝑈𝑂2 + 2𝐻+.
- If uranium is in 𝑆𝑂42− or 𝐶𝑂32− form then you have;

𝑈𝑂2(𝐶𝑂3)34− + 𝐻2 = 𝑈𝑂2 + 𝐶𝑂32− + 2𝐻𝐶𝑂3−

- Note that 𝐻2 reduction to give elemental uranium is not feasible.

- Use of H2O2 in the precipitation of UO22+;

𝐻2𝑂2 + 𝑈𝑂22+ = 𝑈𝑂4 + 2𝐻+

𝑈𝑂22+ + 2𝑁𝐻3 + 3𝐻2𝑂 = (𝑁𝐻4)2𝑈2𝑂7 + 4𝐻+

7.0 ELECTRO-METALLURGY

Introduction
Electrometallurgy refers to the electrolytic processes used to recover and purify metals. It
includes; i. Electrowinning and ii. Electrorefining.

Electrolysis
- Chemical change brought about by an electric current. Results in reactions like;
deposition of metals and evolution of gases.
- Most metals receive electrolytic treatment during their production, either
electrowinning from leach or solvent extraction solutions, or electrorefining from
impure anodes.

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Industrial Electrolysis
Utilizes two separate and equivalent chemical reactions i.e., cathodic reduction and anodic
oxidation.

Electrode Reactions
Processes occurring at the electrodes in an electrolyte under the influence of an electric current.
i. Cathodic reactions.
- Species with the most positive potential are reduced.
a. Metal deposition; Mz+ + ze = M(s)
b. Hydrogen evolution; 2H+ + 2e = H2(g)
c. Reduction reactions; M3+ + e = M2+

ii. Anodic reactions.

- Species with the most negative potentials are oxidized
a. Metal dissolution; M(s) = Mn+(aq) + ne
b. Oxygen evolution; 2H2O = O2(g) + 4H+ + 4e
c. Oxidation reaction; M2+ = M3+ + e - These reactions will depend on the
type of anode.

Electrowinning
- Is an electrolytic extraction process in which the cathodic reduction is used to recover
the sought metal from the electrolyte which is derived from a leaching process.
- Anodes used in the electrolytic cells are usually inert and generally support a gaseous
evolution reaction.
- In aqueous electrowinning processes the anodic reaction is usually oxygen evolution;
2H2O = 4H+ + O2 + 4e
Although in chloride electrolytes, chlorine will usually be evolved; 2Cl - = Cl2 + 2e
- It is desirable that anodes used in aqueous electrowinning be completely insoluble, any
dissolution is likely to produce metal ions which may be reduced cathodically or may
form precipitates which contaminates the depositing metal.
- In fused salt electrowinning, the electrolyte and anode composition determines the
anodic reaction.
- In magnesium extraction, chlorine is evolved but for aluminium a mixture of carbon
monoxide and carbon dioxide.

Cathodes used in aqueous electrowinning

- Are thin sheets of the same metal as that being deposited or you can have stainless steel
or titanium sheets.

Electro-refining
- In an electrolytic refining process, the cathodic reaction is the reverse of the anodic
reaction, hence there is no net cell reaction.
- The impure metal constitute the anode material and dissolves;
M = Mz+ + ze (i)
- At the cathode, metal ions are reduced from solution and deposited;
Mz+ + ze = M (ii)

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 - Anode impurities which have potential more positive than the working anode potential
remain insoluble and form a residue (anode slime).
- Metals with more negative potential, will dissolve anodically with the major metal.
- Electrolytic refining is a two stage purification process in which the elements more
noble than the metal being refined remain insoluble at the anode and elements less noble
dissolves but do not deposit at the cathode - Therefore the depositing metal is thus
purified.

Electrodes in electrowinning Two

types i.e anodes and cathodes.

Anodes
- These operate at positive potential and must be completely insoluble/ inert
- Any dissolution will likely produce metal ions which may be reduced cathodically or
may form precipitates which contaminates the depositing metal.
- Examples include;
i. Pb alloys containing between 5 and 10% antimony. Deficiencies are that it
exhibits some anodic corrosion characteristics and can result in a degree of
cathodic contamination by deposition
ii. 0.06% Ca-Pb alloy- more soluble and is used with solvent extraction copper
electrowinning processes.
iii. Ag-Pb alloys containing up to 0.75% Ag and is used in Zn electrowinning
processes.
iv. Titanium based anodes. These provide good physical mechanical properties in
terms of lower mass per energy consumption and in most cases are used as
platinised titanium.
v. Carbon anodes- exclusively used in electrowinning with fused salt electrolytes
e.g. electrolysis of brine.

Cathodes
- These are used in the form of thin sheets of the metal that is being deposited and are
normally called starter sheets.
- Starter sheets are prepared in special separate electrolytic cells where the metal is
deposited on cathode blanks in which the thin electrodeposited sheets can be readily
stripped.
- The blank surface (cathode blanks) may be wetted with a parting agent to promote
stripping of the starter sheets where stripping can be manual or by use of automatic
stripping machines.
- Cathode dimensions are approximately 950 x 950mm

Suspension loop

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 950

950

Electrolyte
Definition: It is a substance that undergoes partial or complete dissociation into ions in solution
and thus acts as a conductor of electricity. Electrolytes are second-class conductors.

I
1st class (e.g. metals)

2nd class (e.g.𝑁𝑎𝐶𝑙)

During electrolysis, direct current passes into solution through the anode, and leaves through
the cathode. The transfer of electric current through the electrolyte characterized by motion
of charges i.e anions and cations.

Catholyte
The electrolyte surrounding the cathode which is being depleted.

Anolyte
The electrolyte surrounding the anode which is being enriched with metal ions.

Examples
ZnSO4, H2SO4, CuSO4.

Electrolyte quality
- Composition e.g CuSO4 g/L
- Acid e.g. H2SO4 g/L
- Impurities- they reduce the solubility of the salts or electrolytes. Can precipitate As, Ag
Sb using chlorine ions. These impurities can also add to the resistance of the electrolyte.
- Operating temperature- need a high enough temperature to maintain the solubility of
the electrolyte and mobility of ions.
- Circulation and agitation maintains continuous mixing of the electrolyte and minimize
concentration polarization. Flow may be top bottom or bottom top pumping.

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Electrolytic cells and electrode configurations͢
- Cells are precast, reinforced concrete tanks lined with Pb or thermoplastic PVC or HD
polythene.
- In each cell cathodes are arranged alternately with anodes.

- cathode

+ anode

The cathodes are electrically connected in parallel as one (also anodes). The electrolytic cells
are connected in series.

Faraday’s Laws of Electrolysis

Laws gives the relationship between the amount of material liberated or deposited at an
electrode and amount of electrical energy that is passed to the electrolyte.

First Law
States that amount of any substance that is liberated or deposited at an electrode during
electrolysis is proportional to electrical energy passed through the electrolyte.
Mathematically;

WαQ but Q = It
𝐴
→ W α It ∴ W = kIt and k =
𝑛𝐹

Where; W- mass or amount of substance liberated or deposited

Q- amount of electrical charge
I- current (A)
t- time (seconds)
F- Faraday’s constant A-
Relative mass
n- electron equivalent

→ ∴ 𝑊 = 𝐴𝐼𝑡
𝑛𝐹

(A/n)- Chemical equivalence

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Second Law
- When same amount of electricity is passed through different electrolytes, the amount
of different substances deposited or liberated are proportional to the equivalent weight
of the substances.
- 1F (96487C) will discharge A/n
𝐴
- 1C will discharge
96487(𝑛)

𝐴𝐼𝑡
- It coulombs discharge
96487(𝑛)

Current Density
- The operation of an electrolytic plant depends more on the current density than on the
total current, so current is often referred to in terms of current per unit area of the
cathode surface.
- The current density (𝑖) is a measure of intensity of current at the surface of the electrode.

𝐼
𝑖=
𝐴

Where; 𝑖- current density

A- measurable geometric area
I- current

Electrical Conductivity

V = IR

I A

Consider a conductor of length L and area A. The resistance of the conductor is proportional
to the length and inversely proportional to the area i.e. R α L and R α 1/A. Therefore 𝑅 = 𝜌
where ρ is a constant called resistivity (units Ωm)
𝐴

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Current Efficiency (C.E)
C.E of an electrode process is the ratio of the actual extent of the electrode reaction to that
expected theoretically. More importantly for electrowinning processes the cathodic current
efficiency is defined as the ratio of the mass of metal actually deposited to the theoretical
mass that could be deposited in accordance to Faraday’s laws.

𝑎𝑐𝑡𝑢𝑎𝑙 𝑚𝑎𝑠𝑠
% C.E = × 100
𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑚𝑎𝑠𝑠

- Resistivity is a measure of how a substance retards the flow of electric current when an
electric field is applied.
- In between electrodes we have electrolytes, so we should consider the electric field
(V/m);
𝐸
𝑖=
𝜌

Where; E- electric field in V/m. m represents the electrodes spacing.

ρ- resistivity in Ωm
𝑖- current density in A/m2

Decomposition/ Applied potential (VI)

- This is the potential that must be applied to an electrolytic cell to produce current I
through the cell.
- More importantly is the reversible decomposition potential, V o, which is the nominal
potential difference between the anode and cathode that must be exceeded for the
reaction to occur.

Overpotentials
- Activation over potential or polarization, (ηA and ηC ), is the required shift of potential
from the equilibrium value to bring about dissolution or deposition.
- In order to produce a significant amount of current through the cell, increments of
potential are required.
- These include the activation potentials at each electrode and potentials which overcome
the resistance of the electrolyte and various electrical contacts.

- The potential increments are all taken to be positive. The applied potential expression
becomes;
𝑉𝑰 = (𝐸𝑨 − 𝐸𝑪) + 𝜂𝐴 + 𝜂𝐶 + (𝐼𝑅𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑙𝑦𝑡𝑒 + 𝐼𝑅𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑠)
- The electrolyte conductivity is a significant parameter as the IR drop through the
electrolyte may account for some 20 to 30% of the applied potential in electrowinning
and even greater fraction in electrorefining.

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Energy consumption of the system
- The energy consumption per unit mass of metal produced expressed in Kwh/kg of metal
deposited is given by;

Energy consumption = 𝐴 𝑉𝐼𝐹

3600 ×0.01 (𝐶.𝐸)
𝑛
VI – Supplied potential in volts.
F – Faraday’s constant 96500C/ mol
A – Relative mass
C.E - % cathodic current efficiency n
– electron equivalence

26.8 𝑉𝐼
Or simply; Energy consumption =
0.01 (𝐶.𝐸)
𝑛
Optimization aspects
Operating temperature
- High temperature (50 to 70ºC) via steam-heating, to maximize conductivity and
solubility of the metal salt e.g. CuSO4.
- The cell inlet and outlet temperature have a negative temperature differential of 5ºC.
- Temperature increases are limited by;
i. Electrolyte evaporation leading to unhealthy acidic mists. ii.
Increased wear of construction materials.
iii. Increased grain size of cathode deposits→roughness.

Organic additives(Surfactants)
i. Purpose; a) hinders wild growth b) brightens and smoothens cathode deposits.
- Otherwise deposits would be soft, coarse-grained, crystalline or nodular, with a high
susceptibility to entrainment of electrolytes and anode residues. ii. Additives used;
a. Weak solution of bone glue; 1-10ppm in electrolyte at 0.01-0.05kg/tone. b.
Thiourea.
c. Petroleum liquours.
d. Flocculants.

Electrolyte conductivity
- The specific conductivity of typical electrolytes is; k = 0.6 – 0.7 Ω-1m-1
- The electrolyte itself has a resistance and this causes a voltage drop (ohm’s law). The
power consumed is dissipated as heat.

Impurities
- Their concentration should be kept low to avoid decreasing the solubility of the metal
salt. Sources of impurity include; anodic dissolution of non-noble metals and
construction materials.

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Electrolyte composition
- Concentration control is critical for salt solubility, pH, conductivity, cathode deposit
and preferential deposition.

Auxiliary Equipment Circulation

equipment
- Pumps, pipes, delivery pipes, header tanks, collecting and converting solutions, tank for
slimes and reserve electrolyte.
Heating equipment
- Heaters, steam handlers.
Valves Powered equipment
- Overhead cranes, washing machines
Ventilation equipment -
Blowers, fans.
Transformers with rectifiers

Plant operation
Routines include; -
Removing cathodes.
- Stripping cathodes.
- Replacing cathodes with starter sheets.
- Placing new anodes.
- Regular inspections for accretion and short circuits.
- Cleaning out anode slimes that collected at the base of the electrolytic tank.

Control measures -
Production rate.
- Specific energy consumption
- Electrolyte conditions (purity, temperature, circulation rate).
- Cathode current efficiency (C.C.E).
- Cathode current density. - Electrode spacing.
- Short circuit prevention.

Electrolyte handling
- Resistance of electrolyte has to be as low as possible, this can be attained by several
means i.e.;
a. Keeping ionic strength as high as possible, this reduces the chance of other
dissolved metals co-depositing at the cathode.
b. Keep acid concentration at some level. Note that acid is generated in the reactions.
c. Heat electrolyte to maintain optimum temperature.
d. Control the corrosion at anode especially in electrowinning.
e. Control impurity levels via periodical bleeding or alternatively incorporating a
solution cleaning circuit.

Cathodes deposits
- Typical qualities;

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 a. Dense and tightly coherent.
b. Coarse loose crystals.
c. Fine metallic powder.

Factors affecting cathode quality -

Nature of the underlying
metal.
- Electrolyte composition.
- Electrolyte temperature.
- Thickness of deposits formed

Sources of impurities
- From leaching stages.
- Some are naturally occurring impurities and not removed during leaching. -
Some originate from electrode materials.

8.0 GOLD/SILVER HYDROMETALLURGY

Cyanidation
Standard leach process consist of grinding ore to about 80% -200mesh, mixing the slurry with
about 2 pounds per tonne of sodium cyanide and enough lime to keep the pH of the solution at
about 11.0. At a slurry concentration of 50% solids, the slurry passes through a series of
agitated mixing tanks with a residence time of 24hours. The gold bearing liquid is then
separated from the leached solids in thickener tanks or vacuum filters, and the tailings are
washed to remove gold and cyanide prior to disposal. The separation and washing take place
in a series of units by a process referred to as counter current decantation (CCD). Gold is then
recovered from the pregnant solution by zinc precipitation and the solution is recycled for reuse
in leaching and grinding.
Principles of Cyanidation
Various theories have been proposed to explain the mechanism of Au/Ag dissolution in
aqueous cyanide.

Oxygen theory: Elsner (1846) oxygen vital for dissolution of Au/Ag in 𝐶𝑁− solution. Elsner’s
equation

4𝐴𝑢 + 8𝑁𝑎𝐶𝑁 + 𝑂2 + 2𝐻2𝑂 ⇌ 4𝑁𝑎𝐴(𝐶𝑁)2 + 4𝑁𝑎𝑂𝐻

Major Parameters
• Oxygen concentration / partial pressure
• 𝐶𝑁− concentration
• 𝑝𝐻

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Oxygen
Oxygen required for cathodic process to support the anodic dissolution;
𝑂2 + 2𝐻2𝑂 + 4𝑒− = 4𝑂𝐻−
Chemical oxidizers can also be used e.g. 𝑁𝑎2𝑂2, 𝐾𝑀𝑛𝑂7, bromine, chlorine. Adequate
aeration at a lower cost can be used.

Factors affecting 𝑶𝟐 dissolution in 𝑪𝑵− solutions 1.

Temperature of solution.
2. Type and intensity of agitation.
3. Ionic strength of solution.
4. Altitude (barometric pressure).

 At low, [𝐶𝑁−] rate of cyanidation depends on [𝐶𝑁−], 𝑂2 no effect,

 But at high [𝐶𝑁−] it depends on 𝑂2 partial pressure.

- Efficient oxygenation increase rate of cyanidation (saving capital costs) and recovery.
- Also decrease 𝐶𝑁− consumption (by destroying cyanicides)
- Side reactions consuming oxygen detrimental to cyanidation.
e.g. 2𝐹(𝑂𝐻)2 + 12 𝑂2 + 𝐻2𝑂 = 2𝐹𝑒(𝑂𝐻)3

𝑪𝑵− Concentration

Rate Beyond the peak point 𝐶𝑁− hydrolysis

[𝐶𝑁−]

Excess 𝐶𝑁− leads to formation of cyanide complexes of 𝐶𝑢, 𝑍𝑛, 𝐹𝑒 etc. For example;

𝑍𝑛𝑆 + 4𝐶𝑁− ⟶ [𝑍(𝐶𝑁)4] + 𝑆2−

pH
-Keep alkaline to avoid hydrolysis 𝐶𝑁− + 𝐻2𝑂 ⟶ 𝐻𝐶𝑁 + 𝑂𝐻−.
-Alkaline pH also prevents 𝐶𝑁− decomposition by atmospheric 𝐶𝑂2.
𝐶𝑁− + 𝐻2𝐶𝑂3 ⟶ 𝐻𝐶𝑁 + 𝐻𝐶𝑂3− -
Optimum pH range 10 − 11.
 At pH above 9.3 𝐻𝐶𝑁 avoided, you have extensive aurous-cyanide stability field.

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pH Control
- Alkaline pH achieved by adding bases e.g.𝐶𝑎𝑂, soda ash, calcium hydroxide lime and
caustic soda.
- pH indicators and meters used to monitor the levels.

The functions of bases are;

- Prevent loss of 𝐶𝑁− by hydrolysis.
- Prevent loss of 𝐶𝑁− by 𝐶𝑂2 in air.
- Decompose bicarbonates in mill 𝐻2𝑂 before cyanidation.
- Neutralize acidic compounds e.g. ferrous salts, ferric salts and 𝑀𝑔𝑆𝑂4 before
cyanidation.
- Neutralize acidic constituents of ore e.g. pyrite etc.
- Lime promotes settling of fine particles to get clear pregnant solutions.

Cyanide Chemistry
In solution, cyanide exists as either 𝐶𝑁− ions or as hydrocyanic acid (𝐻𝐶𝑁) i.e. dissolved
hydrogen cyanide.
 pH determines relative amounts of the two.
 Low pH favours 𝐻𝐶𝑁.
𝐶𝑁− + 𝐻2𝑂 → 𝐻𝐶𝑁 + 𝑂𝐻− 
At 9.3 pH there is 50% 𝐶𝑁−and 50% 𝐻𝐶𝑁.
 Higher than 9.3 𝐶𝑁− ion dominates and vice versa.
Reaction mechanism
- Reaction electrochemical in nature.
- Oxidising potential provided by reduction of 𝑂2 on 𝐴𝑢 surface.
𝑂2 + 2𝐻2𝑂 + 4𝑒− → 4𝑂𝐻−
- Anodic oxidation of 𝐴𝑢 forming 𝐴𝑢 cyanide complex.
4𝐴𝑢 + 8𝐶𝑁− → 4𝐴(𝐶𝑁)−2 + 4𝑒−

Overall reaction 4𝐴𝑢 + 8𝐶𝑁− + 𝑂2 + 2𝐻2𝑂 = 4𝐴(𝐶𝑁)−2 + 4𝑂𝐻−

Exercise
To dissolve 1 kg of gold how much 𝑁𝑎𝐶𝑁 is required theoretically.

- In practice amount >500 times because of 𝐶𝑁− consumption by other metals and
cyanicides or by loss of 𝐶𝑁− to atmosphere and UV degradation.
- Cyanicides are species of minerals of 𝐹𝑒, 𝐶𝑢, arsenic, antimony and 𝑍𝑛.
- These species also lead to high 𝑂2 consumption.

Temperature
Two things
a. Increase activity of solution & dissolution.
b. 𝑂2 in solution decrease
- Normally around 85ºC optimum.
- If temperature increase then [𝑂2] would decrease.

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- At low [𝐶𝑁−], rate depends on [𝐶𝑁−] but at high [𝐶𝑁−] it depends on 𝑃𝑂2 , so temperature
effects seen at high [𝐶𝑁−].

 Water saturated with 𝐻𝐶𝑁 gas and 𝑂2 attacks gold, with the formation of insoluble
𝐴𝑢𝐶𝑁 and 𝐻2𝑂2.
2𝐴𝑢 + 2𝐻𝐶𝑁 + 𝑂2 ⇌ 2𝐴𝑢𝐶𝑁 + 𝐻2𝑂2

 To avoid 𝐴𝑢𝐶𝑁 formation, alkaline solution needed.

Presence of foreign ions

- Carbonaceous matter if present in 𝐴𝑢 is a source of problem since it adsorb gold - cyanide
complex.
- Metallic minerals that dissolve in 𝐶𝑁− can accelerate or decelerate the gold dissolution.
- Small amounts of 𝑃𝑏, 𝐻𝑔, 𝐵𝑖 and thallium salts accelerates the dissolution.
- They affect electrode potential by promoting a more positive electrode potential.

Film formation on 𝑨𝒖 surface

- Especially if sulphur is present it forms a film. It forms aurous sulphide which protects it
from dissolution.
- Formation of thiocyanate;
𝑆2− + 𝐶𝑁− + 𝐻2𝑂2 + 𝐻2𝑂 = 𝐶𝑁𝑆− + 2𝑂𝐻− + 𝐻2𝑂

Merril - Crowe Process

-
Ore

Leaching (CN )

Clarification

Zinc dust Deaeration

Precipitation Gold

Barren solution

The process starts with filtration of pregnant solution in media filters. Filter types used include
pressure leaf filters, filter presses, and vacuum leaf filters. Generally a precoat of diatomaceous

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earth is used to produce a sparkling clear solution. Clarified solution is then passed through a
vacuum deaeration tower where oxygen is removed from solution. Zinc powder is then added
to the solution with a dry chemical feeder and a zinc emulsification cone. The reaction of the
special fine powder zinc with the solution is almost instantaneous.

2Au(CN)2- + 2e- = 2Au + 4CN - Zn

+ 4CN- = Zn(CN)42- + 2e- 2Au(CN)2- +
Zn = 2Au + Zn(CN)42-
The precipitated gold is then typically recovered in a recessed plate or plate and frame filter
press.

Refractory Ores (Gold)

Termed refractory when direct treatment by cyanidation gives unacceptably low gold
recoveries. Processing uneconomic for the following reasons.
- Gold locked in gangue minerals, often sulphides and cannot be adequately liberated, even
by fine grinding.
- Gold occurs with minerals that consume unacceptable quantities of reagents e.g. pyrrhotite,
arsenopyrite.
- Gold occurs with carbonaceous materials which adsorb gold during leaching. - A
combination of the above can occur.

Refractory ore processing

The common definition of "refractory" gold ores, are those ores that do not allow the recovery
of gold by standard gravity concentration or direct cyanide leaching.
One major category of refractory ores are gold values contained within the crystalline structure
of sulfide minerals such as pyrite and arsenopyrite. For cyanide to leach gold, the cyanide
solution must come into direct contact with gold molecules. With many sulfide ores, the ore
cannot practically be ground down fine enough to expose the gold particles. The objective of
pretreatment for these ores is to remove enough of the sulfide so that at least a small portion of
all gold particles are directly exposed to the elements. Processes available for treatment all
involve oxidation of sulfur to form water soluble sulfates or sulfur dioxide. The main sulfur
oxidation processes include:

1. Bio-oxidation: Bio-oxidation uses sulfur consuming bacteria in a water solution to

remove sulfur.
2. Pressure oxidation: Utilizes oxygen and heat under pressure in a liquid medium, to
effect oxidation of sulfur by way of a controlled chemical reaction. High pressure
autoclaves are used for the reactors. Reactor operation is under alkaline or acidic
conditions, depending upon the specific process.
3. Roasting: Roasting uses heat and air to burn away the sulfur from dry ore. Roasting was
the standard method for sulfur oxidation years ago when it was considered
environmentally acceptable to emit large quantities of sulfur dioxide gas into the
atmosphere. Today’s roasting plants employ elaborate gas scrubbing systems that
frequently produce sulfuric acid as a byproduct.
4. Chemical oxidation using nitric acid at ambient pressure and temperature has also been
used on a limited basis.

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Other ore types considered refractory include:
1. Carbonaceous ores that allow cyanide to dissolve gold but quickly adsorb gold back
onto the active carbon in the ore. Treatment processes include chlorination for carbon
deactivation, roasting to burn away carbon and carbon-in-leach which introduces
competing high activity carbon to preferentially adsorb gold that can be conveniently
separated from the leach slurry.
2. Copper/gold ores that require uneconomically high quantities of cyanide to process due
to the solubility of copper in cyanide.
3. A multitude of other unfavorable constituents including pyrrhotite, tellurides, antimony,
and arsenic.

It should be noted that most of the refractory ore treatment processes are expensive and
frequently economical only with higher grade ores and high processing rates.

Carbon adsorption recovery

Granular coconut shell activated carbon widely used to recover gold from cyanide solutions.
Can be applied to clean solution through fluidized bed adsorption columns or directly to
leached ore slurries by addition of carbon to agitated slurry tanks, followed by separation of
carbon from slurry by coarse screening methods. Gold – cyanide complex adsorbed into pores
of carbon to leave a solution devoid of gold. OH-/CN- hot solution is used to reverse adsorption
and strip carbon. The gold is recovered by electrowinning. The stripped carbon is returned for
reuse.

Variations of the carbon adsorption recovery may include:

1. Carbon-In-Pulp (CIP)
2. Carbon-In-Leach (CIL)
3. Carbon-In-Solution (CIS)

i. CIP
Carbon-in-pulp operation is a variation of the conventional cyanidation process. Ore is crushed,
finely ground, and cyanide leached in a series of agitated tanks to solubilize the gold values.
Instead of separating solids from the pregnant solution, as in the traditional cyanidation
process, granular activated carbon is added to the leached slurry.

The carbon adsorbs the gold from the slurry solution and is removed from the slurry by coarse
screening. In practice, this is accomplished by a series of five or six agitated tanks where carbon
and ore slurry are contacted in a staged countercurrent manner.

This greatly increases the possible gold loading onto the carbon while maintaining a high
recovery percentage. Carbon is retained within the individual CIP tanks by CIP tank screens.
The opening size of the CIP tank screens is such that the finely ground ore particles will pass
through the screens, but the coarse carbon will not. Almost every imaginable type of screen
has been tried for this application, with some types being much more successful than the rest.

ii. CIL
The carbon-in-leach process integrates leaching and carbon-in-pulp into a single unit process
operation. Leach tanks are fitted with carbon retention screens and the CIP tanks are eliminated.

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Carbon is added in leach so that the gold is adsorbed onto carbon almost as soon as it is
dissolved by the cyanide solution. The CIL process is frequently used when native carbon is
present in the gold ore. This native carbon will adsorb the leached gold and prevent its recovery.
This phenomenon is referred to commonly as "preg-robbing". The carbon added in CIL is more
active than native carbon, so the gold will be preferentially adsorbed by carbon that can be
recovered for stripping. The CIL process will frequently be used in small cyanide mills to
reduce the complexity and cost of the circuit.

There are several disadvantages to CIL compared with CIP. Carbon loading will be 20 to 30%
less than with CIP, which means more carbon has to be stripped. (This disadvantage may be
overcome by a hybrid circuit, incorporating a cross between CIL and CIP.) The CIL process
requires a larger carbon inventory in the circuit, which results in a larger in-process tie up of
gold. The larger carbon inventory can also result in higher carbon (and gold) losses through
carbon attrition.

iii. CIS/ Carbon-in-column

With carbon-in-column operation, solution flows through a series of fluidized bed columns in
an upflow direction. Columns are most frequently open topped, but closed top pressurized
columns are occasionally used.

Carbon columns are most commonly used to recover gold and silver from heap leach solutions.
The major advantage of fluidized bed carbon columns is their ability to process solutions that
contain as much as 2 to 3 wt% solids. Heap leach solutions are frequently high in solids due to
fine particle washing from heaps. Down flow carbon columns are rarely used for gold recovery,
because they act like sand filters and are subsequently subject to frequent plugging.

Carbon stripping (Elution) The

major processes include:

i) Zadra Stripping

a. atmospheric

b. pressurized ii) Anglo American Research Laboratory

(AARL) Method iii) Alcohol Stripping iv) Micron

Elution Procedure

i. (a) Zadra (atm)

Atmospheric pressure Zadra stripping was the first commercially successful process developed
for stripping gold from carbon. The process was developed by J. B. Zadra, and others, at the
U.S. Bureau of Mines (USBM) in the early 1950's. The process is still widely used today
because of its simplicity.

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The Zadra process consists of circulating a 1% sodium hydroxide and 0.1% sodium cyanide
water based solution up flow through a stationary bed of loaded carbon at a flow rate of about
2 bed volumes per hour at about 93ºC. Gold that was previously adsorbed on the carbon as a
sodium or calcium/gold cyanide ion pair is desorbed from the carbon by a reversal of the
adsorption kinetics. Gold is recovered from the pregnant strip solution by electrowinning onto
steel wool. The gold depleted solution is then reheated and recycled to the carbon bed for reuse.

The process generally takes about 48 to 72 hours. Typically the gold content of carbon is
reduced from 150 oz Au/ton of carbon to less than 3 oz. Au/ton of carbon.

The Zadra process is characterized by simplicity of system design and operation. Mild steel
equipment is normally used. Manual control is the standard. Fluctuations in flow and
temperatures can reduce stripping efficiency but the only adverse effect is an extension of the
required stripping cycle time. After the desorption vessel has been filled with loaded carbon
and solution flow is started, the only operator attention required is periodic system checks
typical of any process plant operation.

Disadvantages
The main disadvantage of the original Zadra process is its low rate of desorption. It is much
slower than the alternatives. This necessitates larger carbon inventories and larger equipment
than other faster processes.

Stripping temperature is the most significant operating parameter so solutions are kept as close
to boiling temperature as is practical. Since many mines are at high elevations, with resultant
low boiling points, the reduction in stripping rate can be significant when compared with
operations at near sea level altitudes.
Buildup of miscellaneous ions in solution after continued recycling also reduces stripping
efficiency. To alleviate this problem, most operations routinely bleed a fraction of their strip
liquor inventory and replenish with fresh solution.

The efficiency of the electrowinning cells is also significant to stripping efficiency. High levels
of gold in recycled eluant result in a reduction in stripping rate.

(b) Zadra (pressurized)

Zadra process stripping rate could be increased greatly by stripping at higher temperatures. A
comparison of the increase in stripping rate with temperature. To operate at higher
temperatures, the process must operate at pressures higher than the vapor pressure of the
solution. High pressure operation is accomplished by means of a high pressure solution pump
and a stripping column pressure control regulator.

In practice, a solution containing about 1% sodium hydroxide and 0.1% sodium cyanide at
about 280 deg-F and 65 PSIG, is circulated through a pressure vessel filled with loaded carbon
at a flow rate of 2.0 bed volumes per hour. The time required for pressure stripping is generally
from 10 to 14 hours.

Barren strip solution is typically pumped through a heat recovery heat exchanger and a solution
heater. The solution then flows up through the bed of carbon and overflows near the top of the
stripping vessel. The solution is cooled by exchanging heat with barren solution and flows

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through a back pressure control valve, to the pregnant solution holding tank. Pregnant solution
is pumped from the pregnant solution tank through electrowinning cells where gold is
recovered by electrolysis. Barren solution is then returned to the barren solution tank for
recycle (see Figure 4).

High temperature limits are generally constrained by pressure and temperature limitations of
system components, such as vessel design pressures and gasket temperature limits. USBM
research indicated that increases in stripping efficiency could be achieved up to 356 deg-F.
Above 356 deg-F cyanide was decomposed and metallic gold precipitated in the carbon. Plant
practice generally indicates that about 300 deg-F is the upper limit for maximum stripping
efficiency.

Pressure stripping columns are normally sized with a height to diameter ratio of about 4 to 1.
Internal solution distributors and collectors are used to provide even flow of solution
throughout the carbon bed. The majority of pressure strip vessels are constructed from stainless
steel, but many carbon steel vessels are providing satisfactory service.

Solution flow rate has little effect on stripping efficiency in the range of 1 to 4 bed volumes
per hour. Low solution flow rates produce slightly higher efficiencies in most cases, but the
increase is not significant. Stripping efficiency decreases as flow rates are increased above 3
to 4 bed volumes per hour. The design solution flow rate is generally based on a compromise
between reduced elution time and increased equipment costs at higher flow rates.

Most columns are operated with upflow of solution, but some plants have selected to elute by
downflow. The advantage to downflow is reduced potential for binding of flow distribution
screens by tramp material in the carbon. Upflow operation means that the carbon bed is always
flooded, and insures that the carbon is continually contacted by strip solution.
The extent of instrumentation is generally determined by operator preference. Automatic
solution temperature control and column back pressure control are the minimum automation
required.

Solution bleeding is required to prevent the buildup of contaminants, which reduce stripping
efficiency. The amount of solution bleed required varies from about 1/3 of the eluant volume
per cycle, to as low as the residual eluant on the carbon during carbon transfer. Control of the
amount of solution purged from the system is done either on a routine scheduled basis or by
monitoring stripping efficiency and bleeding as efficiency drops.

Operating Schedule:
The following is a typical operating schedule for a Pressure Zadra stripping cycle:

SOLUTION TIME
Load Column Transfer Water 90 minutes
Elution 0.1% NaCN, 1% NaOH 480 minutes
Carbon Cooling Fresh Water 60 minutes
Unload ColumnTransfer Water 30 minutes
TOTAL 11 hours

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ii. AARL Stripping
The Anglo-American Research Laboratories (AARL) stripping procedure (5) was first used on
a large scale in 1980 at the President Brand Gold Mine in South Africa. Since that time, its
application has become standard practice in South Africa and Australia.

The process involves a series of procedures generally starting with an acid wash followed by a
water wash to remove residual acid. The carbon is then soaked for about 30 minutes in a
solution containing about 3% sodium cyanide and 1% sodium hydroxide. High quality fresh
water at about 230 deg-F is then pumped through the pressurized stripping vessel to produce
the pregnant eluant. Gold is recovered from the pregnant eluant by electrowinning and the
barren eluant is discarded.

It is interesting to note that the Zadra stripping procedures researched by the USBM, originally
envisioned presoaking carbon with a caustic cyanide solution followed by elution with
deionized water. This idea was discarded in practice, in favor of the simpler one step caustic
cyanide elution.

The main advantage of the AARL process is the ability to strip a batch of carbon to low gold
residuals in an 8 hour shift. This offers the potential of either designing for multiple stripping
cycles each day and reducing equipment sizes in new plant design, or increasing daily capacity
in existing mills by stripping on additional shifts each day.

Disadvantages of the AARL process include the requirement for high quality water, high water
consumption, the potential for mixing acid with cyanide, and the necessity for automated
controls.

Acid Washing
With the AARL process, elution is normally preceded by acid washing the carbon. Acid
washing is used with all of the other stripping systems, but it is mentioned specifically with the
AARL procedure, because AARL systems generally use the stripping vessel to acid wash and
acid washing is, therefore, controlled as part of the stripping sequence. Acid washing has been
shown to typically increase the efficiency of AARL stripping. Hydrochloric acid is always used
in AARL systems with concentrations generally around 3% by volume.

Acid washing is currently being done both in a separate vessel from the stripping column and
in the elution vessel. Factors favoring acid washing in the elution vessel include: (1)
eliminating a carbon transfer which reduces gold losses from fine carbon breakage of loaded
carbon, (2) conservation of heat if hot acid washing is employed and (3) reduction in stripping
cycle time by eliminating a carbon transfer. Factors favoring installation of a separate acid
wash vessel include: (1) less potential for mixing acid and. cyanide in the event of operator
error or equipment malfunction, and (2) less rigorous requirements for materials of
construction in the stripping circuit since acid proof equipment is not required.

Following acid washing, the carbon is rinsed with fresh water to prevent acid and chlorides
from entering the strip circuit.

Presoak
The presoak step is started by preheating the carbon with hot water. This is followed by soaking
the carbon bed with hot (90 deg-C) 3 WT% NACN/1 WT% NAOH solution for about 30

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minutes. Reduced elution efficiency is experienced if soak solutions concentration are less than
3% NACN but elution rates remain relatively constant with soak solution concentrations above
3% NACN. Changes in the duration of soaking time, for most carbons, has little effect on
stripping efficiency.

Elution
Elution is generally performed using about 6 bed volumes of good quality water at a rate of
about 2 bed volumes/hour.

The quality of water used has a substantial effect on stripping efficiency with the AARL
procedure. The implementation of a hot acid wash step has been shown to reduce water quality
requirements to a certain degree.

The stripping efficiency is virtually independent of eluant water flow rate in the range of 1 to
5 bed volumes per hour. Selection of design and operating flows is made on the basis of
equipment costs and time constraints

Eluant water temperature has a very significant effect on stripping efficiency. Operation at 236
deg-F requires operating pressures of 10 to 15 PSIG to prevent flashing steam in the system.
Operating temperature limits of 236 deg-F are widely specified because of temperature
limitations of the butyl rubber lining material utilized to line the strip vessel. Higher
temperatures also accelerate the decomposition of cyanide.

The last bed volume of eluant water is generally introduced at ambient temperature to cool the
carbon for transfer out of the column.

Process Control
Due to the timed cyclical nature of the procedure, a programmable logic controller (PLC),
automatic pump starting and automatic valves are generally used to time and sequence the
system. Carbon is loaded and transferred manually, but the sequencing of' valves and pumps
during the strip cycle is controlled by the PLC.

Electrowinning
Electrowinning of gold from the pregnant solution is done on a batch basis. The solution pH is
increased to 12 by the addition of sodium hydroxide and electrowinning is started. Solution is
circulated through electrowinning and back to the pregnant solution tank until acceptable
barren levels are achieved. The solution is then discarded.

Operating Schedule:
The following is a typical operating schedule for an AARL stripping cycle:

Solution Time
Load column Carbon 90 minutes
Acid Wash 3% HCl 20 minutes
Water Rinse Potable Water 90 minutes
Potable Water 30 minutes
Pre Heat

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Pre Soak 3%NaCN,1%NaOH 30 minutes
Elution Potable Water 180 minutes
Cooling Potable Water 30 minutes
Carbon Transfer
Transfer Water 30 minutes

TOTAL 7 hours 50 minutes

iii. Alcohol Stripping

Further research at the USBM showed that the atmospheric pressure Zadra stripping cycle can
be made to operate much faster by the addition of alcohol to the strip solution (6).

Figure 6 shows the dramatic laboratory results obtained by adding 20% ethyl alcohol to a Zadra
solution. Several different alcohols were investigated. Methanol, ethanol, and Isopropanol
were all found to increase the gold desorption rate. Ethanol and methanol were found to
perform almost equally, but were substantially better that Isopropanol.

In plant operation alcohol stripping normally requires about 12 to 16 hours to strip carbon to
less than 3 oz. Au per ton of carbon. This is achieved at flow rates in the range of 2 bed volumes
per hour operating in series flow with electrowinning cells.

The main drawback to the alcohol stripping process is the potential for fires. Fires have been
reported at several alcohol stripping operations. The electrowinning section is especially
vulnerable to fires because of the potential for sparks.

Ethanol is generally used rather than methanol. This is due to ethanol's greatly lower health
risks from exposure to vapors. There are, however, isolated examples of operations using
methanol.

Ethylene or propylene glycol are frequently used, rather than alcohol, to increase the speed of
atmospheric pressure Zadra stripping (7). Typical strip times with glycol are 24 to 36 hours.
Glycols are generally used, rather than alcohols, because they are virtually uninflammable. The
disadvantages of glycols are their inferior strip rate increase and higher costs.

A typical glycol stripping solution contains 20 to 25 wt% ethylene or propylene glycol, and 2
wt% sodium hydroxide. Sodium cyanide is sometimes added to the solution but it is frequently
unnecessary. The solution is heated to about 190 deg-F and pumped through the carbon
stripping vessel at a flow rate of about 2 Bed Volumes per hour. Gold and silver values are
recovered from the pregnant solution by electrowinning and the barren solution is reheated and
recycled through the stripping vessel. Glycol consumption is typically in the range of 20 to 40
gallons, per ton of carbon stripped.

iv. Micron Stripping

The most recently developed stripping procedure being used commercially was developed at
Micron Research, in Australia. The Micron method involves pretreatment of loaded carbon,
with a caustic cyanide solution followed by elution with an alcohol mixture.

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The Micron elution procedure takes advantage of the enhanced stripping rate achieved with
alcohol, but confines the alcohol to the closed stripping unit. Fire dangers are reduced quite
substantially, as the pregnant eluant that is subsequently processed for gold recovery does not
contain alcohol.

The elution unit is configured like a packed bed distillation tower with a heater on the base of
the column, an overhead condenser, a reflux pump and the loaded carbon functioning as the
tower packing.

Loaded carbon is first presoaked with sodium cyanide/sodium hydroxide solution. The presoak
solution is drained from the carbon bed and an alcohol solution is added to the vessel.

The unit is then switched to the batch distillation mode. Within a few hours, the alcohol is
concentrated in the overhead condenser tank. The tower bottoms solution is then free of alcohol
and loaded with gold solution which has been stripped by the refluxing action in the column.

The Micron process consists of the following operations:

(1) Presoak
The carbon is first soaked in a solution of 1 to 2 % sodium hydroxide and 5 to 10 % sodium
cyanide at ambient temperature. Carbons with particularly high concentrations of gold, silver,
or copper may require solutions containing up to 20% sodium cyanide. The solution is then
drained from the carbon until free of excess moisture.
(2) Desorption
About 0.5 Bed Volume of alcohol is added after the carbon bed has drained. Methyl alcohol is
used in the majority of applications, but ethanol is occasionally applied. Acetonitrile may be
substituted for the alcohol, but its higher cost generally discourages its use.

Heat is then applied to the base of the desorption vessel. Organic vapors rise through the carbon
bed and are condensed in the overhead condenser. The condensate is pumped back to the top
of the carbon bed and is sprayed on the carbon. The downflowingcondensate washes the gold
values from the carbon particles into the boiler section below.
(3) Alcohol Recovery
When desorption is completed, as indicated by gold solution concentration reaching a constant
level in the column boiler, alcohol recovery commences. The condensate recycle spray is
stopped and the alcohol is allowed to boil out of the pregnant solution. The boiling is terminated
when the temperature in the boiler rises to the boiling point of the water solution. The pregnant
liquor is then drained from the desorption vessel. The carbon is then steam stripped to recover
residual alcohol.

The Micron process produces a very concentrated eluant free of alcohol, with gold and silver
values two or three times higher than those in the loaded carbon. This is in direct contrast with
the Zadra and AARL procedures, which produce eluant concentrations one or two orders of
magnitude lower. The high solution grades make recovery methods such as chemical
precipitation and aluminum foil electro-deposition very attractive.

The micron eluted carbon also appears to have a somewhat higher level of activity than carbon
eluted by other methods. This may reduce the need to reactivate carbon as frequently at some
operations.

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The entire stripping cycle takes about 8 hours. Over 20 licenses for this process have been
issued, but none are in the United States.

Variations
i) Glycol or alcohol are sometimes added to pressure strip or AARL strip operations to
increase stripping rates. ii) A caustic/cyanide presoak may be used in a Zadra system.

iii) A hot water wash is sometimes used at the end of a pressurized Zadra strip to gain some
of the advantage of the water elution used in AARL stripping.

iv) In situations where large amounts of copper load onto carbon with the gold and silver,
a two stage strip may be beneficial. Copper may often be selectively eluted with a cold
caustic/cyanide solution. This is then followed by one of the standard stripping methods.

v) Carbon is normally stripped batch wise, but moving bed continuous elution systems
have occasionally been used with both Zadra and AARL procedures.

vi) Electrowinning may be done under pressure to avoid repressuring solution on each pass
through the carbon. vii) Zinc precipitation may be substituted for electrowinning.

9.0 BASE METALS EXTRACTION

To cover, 𝑍𝑛, 𝐴𝑙, 𝑀𝑔, & 𝐶𝑢

Method of Extraction
Method of extraction depends on; -
Form of mineral (oxide or
sulphide).
- Available technology.
- Cost. Net return on investment.
- Market and market size.
- Legislation-environmental policies. Use of reverberatory furnaces declined because of
impact on global warming.

 Process development, not only about how various processes are done but rather on what is
actually happening and why the processes are carried out in a certain way.
 Understanding show possibilities which exist for future development.

Hydrometallurgy Flow sheet Development

- Processes to be adapted depends on nature of mineral encountered.
- A good process is one that is economic in its use of labour, capital, energy and chemical
reagents.

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 - Correct procedure in any case is that sequence of processes by which metal can be
produced in the desired quality at the lowest overall cost from available ores.
- Sulphides tend to favour pyrometallurgy root, while oxides are either processed by
reductive smelting or hydrometallurgy root.
- Hydrometallurgy root favoured for oxide ore as acid for leaching is relatively cheap.

Common Minerals

Metal Minerals Chemical Formula S.G of mineral

Zinc Sphalerite ZnS 3.9-4.1
Zincite ZnO 5.4-5.7
Marmatite (Fe,Zn)S 3.9-4.2
Aluminium Diaspore Gibbsite Al2O3.H2O 2.3-2.4
Al2O3.3H2O 3.0-3.1
Magnesium Dolomite MgCa(CO3)2 2.8-2.9
Magnesite MgCO3 3.0-3.2
Carnallite KMgCl3.6H2O 1.6
Brucite Mg(OH)2 2.4
Copper Native copper Cu 8.9
Chalcocite Cu2S 5.5-5.8
Covelite CuS 4.6
Chalcopyrite CuFeS2 4.1-4.3
Azurite 2CuCO3.Cu(OH)2 3.8-3.9
Malachite CuCO3.Cu(OH)2 4.0
Chrysocola CuSiO3.2H2O
Cuprite Cu2O 5.9-6.2
Bornite Cu5FeS4 4.9-5.4

Copper
- Sulphides usually treated in pyrometallurgy.
- Oxides easily leachable and hence hydrometallurgy route preferred.
i) Oxides- these occur near surface and are formed by decomposition of primary
sulphide minerals due to action of percolating waters containing 𝐶𝑂2, 𝑂2 and
𝐻2𝑆𝑂4.
- They react with sulphides and produce carbonates, oxides and sulphates and other basic
salts.

ii) Sulphides– are most important ores of 𝐶𝑢. They are complex mixtures of 𝐶𝑢 and
𝐹𝑒 oxides and are mixed with compounds of 𝐹𝑒, 𝑁𝑖, 𝑍𝑛, 𝐴𝑠, 𝑆𝑏, 𝐴𝑔, 𝐴𝑢, 𝑃𝑏, 𝐵𝑖,
𝑇𝑒, 𝑆𝑒.
- Low grade oxidized 𝐶𝑢 ores usually heap leached with 𝐻2𝑆𝑂4 dilute supported by
bacteria.

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Zinc
- Zinc for galvanizing 𝐹𝑒 sheets (sacrificial coating).
𝑍𝑛2+ + 2𝑒− = 𝑍𝑛 𝐹𝑒2+ + 2𝑒− = 𝐹𝑒 -
Zinc tablets (diet trace quantities).
- Alloying 𝑍𝑛 + 𝐶𝑢 = 𝐵𝑟𝑎𝑠𝑠. - Anti-rust paints.
- 𝐴𝑢 cementation.

- Common ore mineral is sphalerite (𝑍𝑛𝑆). Mineral tends to be associated with 𝑃𝑏,
𝐶𝑢, 𝐴𝑔, 𝐼𝑟, 𝐺𝑒,𝑇ℎ.
- ZnS no direct smelting.
- ZnS conversion to oxides by roasting.
1
𝑍𝑛𝑆 + 𝑂2 = 𝑍𝑛𝑂 + 𝑆𝑂2 sulphatised 𝑍𝑛𝑂 + 𝑆𝑂2 + 2 𝑂2 = 𝑍𝑛𝑆𝑂4
- ZnO/ ZnSO4 leachable.

Aluminium
Gibbsite (𝐴𝑙2𝑂3 ∙ 3𝐻2𝑂)

Ore bauxite Bohmite 𝐴𝑙2𝑂3 ∙ 𝐻2𝑂

Principal ore
Gangue (oxides of 𝑆𝑖, 𝐹𝑒, 𝑀𝑔 e.t.c.)
Leaching done (Bayer process) to produce pure 𝐴𝑙2𝑂3(Alumina)
This is then sent to the electrolytic refining Hall Heroult process and the Hoopes process

Magnesium
- Aluminium alloys to increase strength and corrosion resistance.
- Desulphurisation in the iron blast furnace.
- Cathodic protection.
- As a reagent in petrol processing.

• Naturally occurring 𝑀𝑔 containing brines are concentrated in large ponds by solar

Evaporation.
• Extraction: they are two routes : i. Electrolysis of magnesium chloride and ii. Thermal
reduction of magnesium oxide.

Bacterial Leaching
- Dump, heap and stope leaching of 𝐶𝑢 normally involve bacterial leaching processes.
- Environment altered to optimize bacteria activity.
- Height of dump ~9m inorder to avoid excessive 𝑡𝑜within the dump (≯ 500𝐶).
- Ventilation maximized to offer adequate 𝑂2 to bacteria.
- Optimum temperature~350𝐶.
- Bacteria loose activity at temperatures >45°𝐶.
- Also applied in stope and heap leaching of uranium ores.

Copper Electrowinning
- Carried out from acid sulphate solutions containing 𝐶𝑢2+ ions.

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 - Electrolytes obtained from leaching.
- Because of impurities present in pregnant solution solvent extraction done for
electrolyte purification.
- Impurities e.g. 𝐹𝑒3+ reduce current efficiency (C.E). 𝐹𝑒3+ + 𝑒 → 𝐹𝑒2+. 𝐹𝑒2+ reoxidized
at the anode back to 𝐹𝑒3+.
- Especially in dump and heap leaching 𝐹𝑒 content high. Solvent extraction E/W done.
- Cathode: 𝐶𝑢2+ + 2𝑒 = 𝐶𝑢(𝑠)
- Electrolytes produced by stripping stage normally 30 − 55𝑔𝑙−1 𝐶𝑢 and 135 −
150𝑔𝑙−1 𝐻2𝑆𝑂4.
- Spent electrolytes recycled to stripping: 25 − 30𝑔𝑙−1 𝐶𝑢 and 150−185𝑔𝑙−1 𝐻2𝑆𝑂4.

ORE

LEACHING

Pregnant solution
barren
solution
EXTRACTION

Loaded organic phase

loaded org
STRIPPING

Spent
Electrolyte E/W Metal (Cathode Copper)

- Electrolyte temperature of 25°C to 45°C.

- Applied pot 2.0V per cell 𝑉1 = 𝑉° + 𝜂𝐴 + 𝜂𝐶 + 𝐼𝑅 𝑑𝑟𝑜𝑝(𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 + 𝑐𝑜𝑛𝑡𝑎𝑐𝑡𝑠) =
0.89+< 0.5 + 0.05+< 0.5 + ~0.1 =≯ 2.04𝑉
- Nodules growth-due to imperfections on starting sheets or from the adhesion of
particles suspended in solution.
- Short circuiting can result.
- Periodic current reversal (PCR) done to avoid that.
- Energy consumption increase but benefits of smooth cathode achieved. -
Electrowinning can also be done from chloride solutions.

Electrolysis of Igneous Fusions

- Used for the electro-winning of reactive metals which cannot be effectively deposited
from aqueous solution because 𝐻2 evolution is the dominant reaction.

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 - Metal oxide or salt is dissolved in a fused salt electrolyte.
- Indication of minimum potential for cell reaction at a particular temperature given by
standard free energy of formation of compound as:
- ∆𝐺° = −𝑍𝐹𝐸°
- 𝐸° = Reversible decomposition potential(Vo)
- Practically it is not useful because it does not include over potential components and
potential to overcome electrolyte and contact resistances.
- Actually 𝑉° can be as high as 6V for effective metal deposition.
- This is because of a high 1R drop through electrolyte and significant contact resistances
to be overcome.
- Electrolyte should have a low melting point and be able to dissolve metal salt.
- Solubility of reduced metal in electrolyte must be negligible and s.g sufficiently
different to effect physical separation.

Electro-refining with fused salt electrolytes

- Processes operate at high temperatures and therefore expensive so only used when it is the
only route or when it offers significant merits.
- Aluminium has found commercial use of this process.

Electrolysis of Aluminium a. The Hall Process: E/W

- Is the electrowinning of aluminium obtained from the leaching process e.g. from
the bayer process.

b. The Hoopes Process

- Process used to electro-refine aluminium from the electrowinning stage.

[Group presentations on the topics]

Magnesium Extraction

Introduction
Magnesium (Mg) is a silvery white metal that is similar in appearance to aluminum but weighs
one-third less. With a density of only 1.738 grams per cubic centimetre, it is the lightest
structural metal known. It lacks ductility when worked at lower temperatures. In addition, in
its pure form, it lacks sufficient strength for most structural applications. However, the addition
of alloying elements improves these properties to such an extent that both cast and wrought
magnesium alloys are widely used, particularly where light weight and high strength are
important.

Magnesium is strongly reactive with oxygen at high temperatures; above 645° C (1,190° F) in
dry air, it burns with a bright white light and intense heat. For this reason, magnesium powders
are used in pyrotechnics. At room temperature, a stable film of water-insoluble magnesium
hydroxide forms on the metal’s surface, protecting it from corrosion in most atmospheres.
Being a strong reactant that forms stable compounds with chlorine, oxygen, and sulfur,
magnesium has several metallurgical applications, such as in the production of titanium from
titanium tetrachloride and in the desulfurization of blast-furnace iron. Its chemical reactivity is

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also evident in the magnesium compounds that have wide application in industry, medicine,
and agriculture.

Mining and concentration

Both dolomite and magnesite are mined and concentrated by conventional methods. Carnallite
is dug as ore or separated from other salt compounds that are brought to the surface by solution
mining. Naturally occurring magnesium-containing brines are concentrated in large ponds by
solar evaporation.

Extraction and refining

Magnesium forms stable compounds and reacts with oxygen and chlorine in both the liquid
and gaseous state. This means that extraction of the metal from raw materials is an
energyintensive process requiring well-tuned technologies. Commercial production follows
two completely different methods: electrolysis of magnesium chloride or thermal reduction of
magnesium oxide. Where power costs are low, electrolysis is the cheaper method—and,
indeed, it accounts for approximately 75 percent of world magnesium production.

Electrolysis
Electrolytic processes consist of two steps: the preparation of a feedstock containing
magnesium chloride and the dissociation of this compound into magnesium metal and chlorine
gas in electrolytic cells.

In industrial processes, cell feeds consist of various molten salts containing anhydrous
(essentially water-free) magnesium chloride, partly dehydrated magnesium chloride, or
anhydrous carnallite. In order to avoid impurities present in carnallite ores, dehydrated artificial
carnallite is produced by controlled crystallization from heated magnesium- and potassium-
containing solutions. Partly dehydrated magnesium chloride can be obtained by the Dow
process, in which seawater is mixed in a flocculator with lightly burned reactive dolomite. An
insoluble magnesium hydroxide precipitates to the bottom of a settling tank, whence it is
pumped as a slurry, filtered, converted to magnesium chloride by reaction with hydrochloric
acid, and dried in a series of evaporation steps to 25 percent water content. Final dehydration
takes place during smelting.

Anhydrous magnesium chloride is produced by two principal methods: dehydration of

magnesium chloride brines or chlorination of magnesium oxide. In the latter method,
exemplified by the IG Farben process, lightly burned dolomite is mixed with seawater in a
flocculator, where magnesium hydroxide is precipitated out, filtered, and calcined to
magnesium oxide. This is mixed with charcoal, formed into globules with the addition of
magnesium chloride solution, and dried. The globules are charged into a chlorinator, a
bricklined shaft furnace where they are heated by carbon electrodes to approximately 1,000°–
1,200° C (1,800°–2,200° F). Chlorine gas introduced through portholes in the furnace reacts
with the magnesium oxide to produce molten magnesium chloride, which is tapped at intervals
and sent to the electrolytic cells.

Dehydration of magnesium brines is conducted in stages. In the Norsk Hydro process,

impurities are first removed by precipitation and filtering. The purified brine, which contains
approximately 8.5 percent magnesium, is concentrated by evaporation to 14 percent and

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converted to particulates in a prilling tower. This product is further dried to water-free particles
and conveyed to the electrolytic cells.

Electrolytic cells are essentially brick-lined vessels equipped with multiple steel cathodes and
graphite anodes. These are mounted vertically through the cell hood and partially submerged
in a molten salt electrolyte composed of alkaline chlorides to which the magnesium chloride
produced in the processes described above is added in concentrations of 6 to 18 percent. The
basic reaction is:

Operating temperatures vary from 680° to 750° C (1,260° to 1,380° F). Power consumption is
12 to 18 kilowatt-hours per kilogram of magnesium produced. Chlorine and other gases are
generated at the graphite anodes, and molten magnesium metal floats to the top of the salt bath,
where it is collected. The chlorine can be reused in the dehydration process.

10.0 REFERENCES
1. E. Jackson, Hydrometallurgical extraction and reclamation
2. F. Habashi, A textbook of hydrometallurgy
3. A. R. Burkin, Chemical hydrometallurgy, theory and principles
4. LC Woollacott and RH. Eric, Mineral and metal extraction an overview

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 5. C. K. Gupta and TK. Mukherjee, Hydrometallurgy in extraction processes
6. JO. Marsden and CI. House, The chemistry of gold extraction
7. Wills, B.A. 1997. Mineral Processing Technology, 6th Edition, ButterworthHeinemann,
Johannesburg.
8. Woollacott, L.C., Eric, R.H. Mineral and Metal Extraction An overview, Monograph
Series M8, The South African Institute of Mining and Metallurgy, Johannesburg, 1994.
9. Summary Report: Control and Treatment Technology for the Metal Finishing Industry
Ion Exchange USEPA EPA 625/-81-007 June 1981 pp 4-10 (updated by Remco
Engineering).
10. Coulson and Richardson, Chemical Engineering, 5th edition, Butterworth-Heinemann,
Johannesburg.
11. Denver Mineral Engineers, The basic processes of gold recovery and carbon stripping,
the practical alternatives.

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