Section

4
Introduction to Hydrometallurgy
Specific Objectives
To be able to discuss and answer questions on the following:
Typical hydro processing steps (with examples):
Pretreatment
Leaching reactions and techniques
Solution purification and concentration
Metal recovery
Electrorefining
Leach regeneration and reagent recovery
Practical considerations in selecting a hydro process.


Reference
Rosenqvist T, 1983. Principles of Extractive Metallurgy, 2nd. Edition, 506 pages
(McGraw-Hill: New York), ISBN 0 07 053910 3.
















Introduction to Hydrometallurgy v2013 1
PROCESSING STEPS IN HYDROMETALLURGY
Most hydrometallurgical processes can be divided into five main steps as shown in the
following diagram, followed by residue treatment and possibly byproduct recovery.
The important steps will be discussed in more detail.


Leaching
Solid/Liquid Separation

Leach Regeneration /
Reagent Recovery

Solution Purification/
Concentration

Pretreatment
Residue Treatment
Tailings Disposal
Ore
Metal or Product
Recovery
Product
Makeup
Reagent
Pure / Concentrated
Solution
Impurities
Additives for
Purification
Liquor
Recyle

Figure 1. Typical Hydrometallurgical Processing Steps

1. Pretreatment
Pretreatment steps can be either (1) physical processes such as grinding,
concentration (e.g. flotation) or agglomeration or (2) chemical processes such as
roasting.
1.1 Physical Processes
1.1.1 Concentration
Hydro processes are normally most suitable for ores which cannot be concentrated.
However two commercial examples where concentration is used are in the
Roast/Leach/Electrowin process for zinc production, which involves the production of
a ZnS concentrate by flotation as the first step, and also the CLEAR process for
copper which uses flotation to produce a copper sulfide concentrate as the first step.

1.1.2 Agglomeration
In the leaching of low grade ores, the reagent is often percolated through heaps (heap
leaching). If fines, clays or slimes are present these can block channels and stop
reagent flow. The process can be greatly improved by agglomeration of fines into
porous pellets or balls by mixing with cheap binders such as lime or cement.
Introduction to Hydrometallurgy v2013 2
1.1.3 Grinding
Grinding of ores liberates the valuable mineral and makes it more accessible to the
leach solution. However, size reduction (especially fine grinding) is expensive and
becomes prohibitively so as the grade of the ore decreases.
1.2 Chemical Alteration
This can either be by gas/solid reaction (roasting) or by liquid/solid reaction.
1.2.1 Roasting
Some roasting processes have been considered in the introduction to pyrometallurgy
lecture. Some of the more important commercial applications are summarised here:
Roasting of ZnS: Air is used at 600
o
C to produce ZnO, which is easier to leach than
ZnS, for subsequent leaching in sulfuric acid:
2ZnS + 3O
2
2ZnO + 2SO
2
(g)
Roasting of Auriferous Pyrite: In many major deposits, gold is associated with iron
sulfides such as pyrite (FeS
2
), from which it is often difficult to leach. Roasting in air at
600
o
C results in an insoluble porous iron oxide calcine from which gold can be readily
leached using cyanide solution.
Au/FeS
2
+ O
2
Au + Fe
2
O
3
+ SO
2
(g)
Roasting of Nickel Laterites: Nickel laterites contain around 1.5% Ni (actually as
complex oxides such as (Fe,Ni)O(OH) but unlike sulfide ores cannot be upgraded by
mineral processing. The Caron process involves an initial reducing roast at around
900
o
C using coal or oil, followed by leaching of the resultant nickel metal in
ammoniacial liquor (e.g. Greenvale in Qld). The reduction reaction can be idealised
as:
2NiO + H
2
+ CO 2Ni + H
2
O + CO
2

A number of other roasting processes are used on a smaller commercial scale. These
include:
Segregation roast: Low grade copper oxide ores are difficult to concentrate and are
treated hydrometallurgically, usually by leaching with sulfuric acid. One different
process involves so-called "segregation roasting" in which the ore and a small amount
of salt (NaCl) and carbon are heated at around 600
o
C. A complex reaction occurs
and copper is concentrated by migrating onto carbon where it is reduced to its metallic
form. The calcine is screened to separate carbon and the copper recovered from it by
leaching. This complex reaction can be idealised by:
CuO + C
NaCl
Cu(on carbon) + CO(g)
Becher Process: Ilmenite (FeTiO
3
) from mineral sands, can be upgraded into
synthetic rutile TiO
2
by removal of iron. An important method is the Becher Process
developed in W.A. Ilmenite is firstly roasted in air to oxidize all iron to Fe
3+
, and then
with coal to reduce it to metallic Fe, which is finally removed by accelerated "rusting" to
Fe
2
O
3
in aerated water. This complex process can be idealised as:
FeO.TiO
2

roast air
Fe
2
O
3
.TiO
2
+ TiO
2

roast C
Fe + TiO
2
Introduction to Hydrometallurgy v2013 3
Sulfation Roast: Copper and cobalt sulfides can be converted into water soluble
sulfates by roasting at 600
o
C in air under closely controlled conditions, such that the
iron impurities remain as insoluble ferric oxide. The valuable sulfates can then be
preferentially leached in dilute sulfuric acid. Sulfation roasting of chalcopyrite can be
idealised as:
CuFeS
2

Air /SO
2
CuSO
4
+ Fe
2
O
3
+ SO
2
(g)
1.2.2 Solid/Liquid Reaction
A commercial example is "pug-roasting" in which oxides are heated with concentrated
sulfuric acid to produce water soluble sulfates in a highly exothermic reaction. For
example, in the sulfate process for the production of TiO
2
from ilmenite, ilmenite is first
pug-roasted at 100-200
o
C with concentrated H
2
SO
4
to yield a honeycombed mass
of iron and titanium sulfates which are then dissolved in water:
FeTiO
3
+ 2H
2
SO
4
TiO.SO
4
+ FeSO
4
+ 2H
2
O
Other examples which have not yet been used commercially include the roasting of
CuFeS
2
with S to produce Cu
2
S which is more easily leached (than CuFeS
2
) and the
treatment of complex Cu/Pb sulfides with sulfuric acid to produce sulfates.
2. Types of Leaching Reactions
In general, commercial leaching reactions can be classified into the following main
types: water salvation, acid attack, alkali attack, complexation and oxidation (often with
complexation).
2.1 Water solvation
Water solvation refers to the dissolution of naturally soluble salts in water, such as
CuSO
4
or CoSO
4
from sulfation roasting:
CuSO
4(s)
Cu
2+
(aq)
+ SO
4
2
(aq)

These ions are actually solvated (=complexed) with water molecules and the usual
convention (not followed here for convenience) is to indicate this by Cu
2+
(aq) and
SO
4
2
(aq).
2.2 Acid attack
Most important examples are the dissolution of ZnO calcine (with subsequent
electrowinning) with sulfuric acid and the leaching of low grade copper oxide ores also
with sulfuric acid (the latter accounts for the majority of copper extracted by
hydrometallurgy). Reactions are simple:
ZnO + 2H
+
Zn
2+
+ 2H
2
O
CuO + 2H
+
Cu
2+
+ 2H
2
O

where the spectator ion is SO
4
2
in both cases.
2.3 Alkali attack
Most important example is the Bayer Process which begins with the dissolution of
bauxite using NaOH:
Introduction to Hydrometallurgy v2013 4
Al(OH)
3
+ OH

Al(OH)
4

where the spectator ion is Na
+
.
2.4 Complexation
Most commercial leaching reactions which involve complex ion formation also involve
oxidation and are included below.
2.5 Oxidation
Solids can be brought into solution by oxidation (=anodic reaction) which involves the
loss of electrons. This must be accompanied by reduction (= cathodic reaction) within
the leach solution to absorb the electrons. Anodic reactions of industrial importance
involve either the oxidation of metals (=corrosion) or the oxidation of sulfur contained
in sulfides. The most important cathodic reactions are those using either dissolved
oxygen or ferric ions as oxidants (= electron absorbers) in leach solutions.
Industrial Anodic Reactions (Oxidation)
Oxidation of Metals
Au Au
+
+ 1e

(Leaching gold in NaCN) (1)

U
4+
U
6+
+ 2e

(Leaching of uranium oxide) (2)

Ni Ni
2+
+ 2e

(Caron Process for low grade Ni ores) (3)

Oxidation of Sulfur
S
2
S
0
+ 2e

(CuFeS
2

for Heap Leaching & CLEAR process) (4)
(Direct acid pressure leaching of ZnS) (5)
S
2
S
6+
+ 8e

(Pressure oxidation NiS & ZnS) (5)

Industrial Cathodic Reactions (Reduction)
(a) Oxygen Gas in Water (O
0
+ 2e

O
2
)
O
2
(g) + 4H
+
+ 4e

2H
2
O (6a)
or, in less acidic solution,
O
2
(g) + 2H
2
O + 4e

4OH

(6b)
(b) Ferric Ions
Fe
3+
+ e

Fe
2+
(7)
Oxygen is the most powerful oxidant and is in plentiful supply in the atmosphere but
this reactant must still be supplied and dissolved in the solution to maintain the
necessary oxygen levels in the reactor. An alternative is to use ferric ions to absorb
electrons but only in acid solutions since ferric hydroxide will precipitate otherwise.
Ferric ions often act as intermediates during acidic oxidation, that is, electrons are
absorbed through (7), but the ferrous ions are reoxidised to ferric by oxygen through
reaction (6a). The end result is equivalent to aerial oxidation but via ferric ions.
Introduction to Hydrometallurgy v2013 5
Complete Leaching Reactions (oxidation plus reduction)
1. Leaching of gold
Gold occurs mainly in the metallic form and is leached via reaction (1) which is carried
out in the presence of CN

(added as NaCN or KCN) since this forms a stable

complex and thus improves gold solubility. Complex formation may be written as:
Au + 2CN

Au(CN)
2

+ e

(8)
Air is used as the oxidising agent. Reactions (1) and (8) are combined to eliminate the
electrons and give the process reaction as:
4Au + O
2
+ 2H
2
O + 8CN

4Au(CN)
2

+ 4OH

(9)
where sodium is a spectator ion.
2. Leaching of uranium oxide
Uranium mainly occurs in low grade oxide ores as mixtures of UO
3
(U as U
6+
) and UO
2
(U as U
4+
)
.
UO
3
can be directly dissolved as the complex ion UO
2
2+

(e.g. as
UO
2
(SO
4
)
2
2-
) but the tetravalent ion

in UO
2
must firstly be oxidised before it will
dissolve. Reaction (2) is usually carried out in the presence of H
2
SO
4
, which allows the
formation of the stable UO
2
(SO
4
)
2
2-
complex although Na
2
CO
3
is sometimes used
with the formation of the UO
2
(CO
3
)
3
4-

complex. The reaction for sulfuric acid is:
UO
2
+ 2SO
4
2
UO
2
(SO
4
)
2
2
+ 2e

(10)
Air is commonly used as an oxidant (although Fe
3+
/Fe
2+
acts as an intermediate).
Acid leaching can thus be described by a combination of reaction (6a) with (10):
UO
2
+ O
2
+ 2SO
4
2
+ 2H
+
UO
2
(SO
4
)
2
2
+ H
2
O (11)
3. Leaching of Low Grade NiO Ores in Caron Process
After reduction roast of NiO to Ni, the metal is dissolved in an oxidative leach in the
presence of ammonia in order to form the stable complex Ni(NH
3
)
6
2+
. Reaction (3)
then becomes:
Ni + 6NH
3
Ni(NH
3
)
6
2+
+ 2e

(12)
Air is used as the oxidant and the process in this basic solution is best described by a
combination of reactions (12) and (6b):
Ni + 6NH
3
+ O
2
+ H
2
O Ni(NH
3
)
6
2+
+ 2OH

(13)
4. Leaching of Chalcopyrite (CuFeS
2
)
Chalcopyrite is leached industrially either in the form of low grade ores or as
concentrates where reaction (4) can more completely be written as:
CuFeS
2
Cu
2+
+ Fe
2+
+ 2S
o
+ 4e

(14)
Some further oxidation of S
o
to S
6+
(as SO
4
2
) often takes place.
Introduction to Hydrometallurgy v2013 6
Low Grade Ores: These are "heap" leached on site using sulfuric acid (which will
also leach any oxide present) with ferric ions as oxidant. A combination of (14) and (7)
describes the process.
CuFeS
2
+ 4Fe
3+
Cu
2+
+ 6Fe
2+
+ 2S
o
(15)
where SO
4
2

is a spectator ion.
This process is known as bacterial leaching since bacteria (in particular Thiobacillus
ferroxidans) play an important role by reoxidising Fe
2+
back to Fe
3+
much faster than
normal aerobic oxidation (= in presence of air). Since this reoxidation process
replenishes the supply of ferric ions, reaction (15) is driven forward. These bacteria
can also oxidise S
o
to S
6+
resulting in the formation of sulfate SO
4
2
.
Chalcopyrite Concentrates: Most chalcopyrite concentrates are processed by
pyrometallurgy despite many attempts to develop leaching processes. The so

called
CLEAR process (for Copper, Leach, Electrolysis and Regeneration) is a recent
commercial attempt at a hydro process in which chalcopyrite is essentially leached
with a solution of ferric chloride through reaction (7). Dissolution of the sulfide involves
both the oxidation of S
2

through reaction(4) and the reduction of Cu
2+
to Cu
+
in the
presence of excess Cl

ions (from NaCl saturation) to form the stable complex CuCl
2

since CuCl alone has poor solubility in water:
CuFeS
2
+ 2Cl

CuCl
2

+ Fe
2+
+ 2S
o
+ 3e

(16)
The oxidation with ferric ion as oxidant can be described by a combination of (16) with
(7):
CuFeS
2
+ 2Cl

+ 3Fe
3+
CuCl
2

+ 4Fe
2+
+ 2S
o
(17)
where Cl

is a spectator ion. (The process is actually a little more complicated because

the reduction of Cu
2+
to Cu
+
is necessarily coupled with an oxidation of S
2

to S
o
,
and in fact extra cupric chloride is added to act as an oxidant in addition to ferric
chloride.)
5. Oxidation Leaching of Zinc Sulfide
At present, the vast majority of zinc sulfide is firstly roasted to ZnO and then leached
with sulfuric acid. However, a recent commercial process involves a one step leach
using pressure oxidation with air and dissolution in H
2
SO
4
all at 200
o
C. Zinc is
dissolved as the sulfate and elemental sulfur is formed. Reaction (4) thus becomes:
ZnS Zn
2+
+ S
o
+ 2e

(18)
With air as the oxidant, the process can be described by a combination of (18) and
(6a).
ZnS + 1/2O
2
+ 2H
+
Zn
2+
+ S
o
(19)
where SO
4
2

is a spectator ion.
6. Leaching of Nickel Sulfide (Sherritt Gordon Process)
Introduction to Hydrometallurgy v2013 7
Nickel sulfide is oxidised with air under pressure in the presence of ammonia to form
the stable complex Ni(NH
3
)
6
2+
. Sulfur in NiS is oxidised from S
2
to S
6+

which exists in
the solution as SO
4
2
. Reaction (5) for this process is thus more completely
represented by:
NiS + 4OH

+ 6NH
3
Ni(NH
3
)
6
2+
+ SO
4
2
+ 4H
+
+ 8e

(20)
Since oxidation is by air, the process can be described by a combination of (20) with
(6a):
NiS + 2O
2
+ 6NH
3
Ni(NH
3
)
6
2+
+ SO
4
2
(21)
This description idealizes the process a little since the concentrate contains iron as
well as nickel and not all sulfur is initially oxidised through to SO
4
2
.
3. Leaching Techniques
A range of techniques and a variety of equipment are employed for leaching, namely:
in-situ leaching, dump and heap leaching, percolation leaching, pulp (slurry) leaching.
3.1 In-situ leaching refers to either the leaching of ore left in a mine after it has been
worked out or to the direct leaching of an ore body in the ground, usually after it has
been shattered by explosives. The leach solution is introduced above the ore body
and allowed to percolate by gravity before being collected at lower levels by a network
of sumps. It is then pumped to the surface and processed for metal recovery. The
method has been applied to low grade copper and uranium ores, and although the
cost of mining is cheap, these savings may be offset by low extraction rates and
efficiencies and the loss of leach liquor into the ground water.
3.2 In dump or heap leaching, fractured rock (0.11 m) is removed from the mine and
piled, without further size reduction, onto a prepared impervious terrain. The leaching
agent is applied at the top of the pile and then collected at the bottom for metal
recovery giving typical extraction efficiencies of 60%. This is an important method for
the treatment of low grade copper and uranium ores and the flow sheet used will be
discussed in more detail later.
3.3 In percolation leaching, ore is coarsely crushed (to 520 mm) and charged into
large vats having false bottoms. Countercurrent leaching is usually employed to
ensure extraction efficiencies of around 80%. Once the ore is spent, the vats are
emptied mechanically and the process repeated. Applications are for copper, gold and
uranium.
3.4 Pulp or slurry leaching involves the leaching of finely milled ores (200 mm) in
agitated and usually aerated vessels, at either atmospheric pressure in open vats or at
higher pressures in sealed autoclaves. The additional costs of these techniques limit
their application to high value metals (e.g. gold cyanidation in open vats) or to
concentrated minerals (e.g. NiS and ZnS oxidation in autoclaves). Open vats may be
agitated by injection of compressed air at the bottom (pachuca tanks) or mechanically
using paddles or rakes (low turbulence) or propellors and turbines (high turbulence).
Autoclaves may also be agitated by compressed air or mechanically.
4. Solution Purification and Concentration
Leach solutions may be treated directly to recover their metal values. Or they may first
have to be purified and concentrated before the metal values can be recovered
Introduction to Hydrometallurgy v2013 8
efficiently. Many impurities are themselves valuable and are often recovered in
separate byproduct stream(s).
4.1 Impurity removal
Two important methods are used, namely (i) cementation, which is based on metal
displacement using the electrochemical series and (ii) precipitation of insoluble salts
such as sulfides, hydroxides, sulfates and carbonates, which is based on the classical
table of group separation of metal ions (recall solubility products of metals) developed
by inorganic and analytical chemists. The processes of solvent extraction and ion
exchange can also be used and continue to offer new purification possibilities, but
these are still mainly used for concentration and will be discussed below.
4.1.1 Cementation
e.g. Removal of Cu, Cd and Ni from zinc leach solutions by the addition of zinc dust:
Cu
2+
+ Zn Cu + Zn
2+

Cd
2+
+ Zn Cd + Zn
2+

Ni
2+
+ Zn Ni + Zn
2+

4.1.2 Precipitation of insoluble compounds
Sulfide Precipitation: e.g. Removal of Co and Cu by the addition of H
2
S gas:
Cu
2+
+ H
2
S CuS(s) + 2H
+

Co
2+
+ H
2
S CoS(s) + 2H
+

Hydroxide Precipitation: e.g. Removal of iron and tin by pH adjustment:
Fe
3+
+ 3H
2
O Fe(OH)
3
+ 3H
+
pH = 3
Sn
4+
+ 4H
2
O Sn(OH)
4
+ 4H
+
pH = 1
Note: The reactions can also be written in the form Fe
3+
+ 3OH

Fe(OH)
3
by
combining these equations with the associated water equilibrium, H
+
+ OH

= H
2
O,
but it is more descriptive to write equations including H
+
when dealing with acid
solutions (i.e. pH < 7).
Sulfate Precipitation: e.g. neutralisation of acidified sulfate solution using lime, prior to
effluent disposal:
Ca(OH)
2
+ SO
4
2
+ 2H+ CaSO
4
.2H
2
O(s)
Carbonate Precipitation: e.g removal of lead by addition of a soluble carbonate:
Pb
2+
+ CO
3
2
PbCO
3
(s)
4.2 Concentration
This is achieved by selective extraction of the valuable metal ion from low grade leach
solutions by "loading" into an ion specific organic solvent (solvent extraction) or onto
an ion specific resin (ion exchange). Once the exchange media is fully loaded, it is
separated from the leach solution and the valuable ion chemically stripped from it in a
process called "elution". The exchange media is regenerated for use in another
process cycle and the valuable ion collected in a more concentrated solution, ready for
subsequent recovery. Ion exchange and especially solvent extraction have become
Introduction to Hydrometallurgy v2013 9
well established since their first large scale application for uranium recovery during
World War 2 and are now used not only for costly metals, such as uranium, vanadium,
niobium, tantalum and zirconium but also for less costly metals such as copper and
zinc.
4.2.1 Ion Exchange (IX)
For example, concentration of uranium from low grade leach solutions. Uranium is
present in acid leach solutions mainly as UO
2
(SO
4
)
2
2

. If an aqueous solution
containing this anion is brought into contact with an anion exchange resin (i.e. a resin
on which the anion is loosely bound), the following anion exchange equilibrium will be
established:
2R
+
X

+ UO
2
(SO
4
)
2
2

[R
+
]
2
UO
2
(SO
4
)
2
2

+ 2X

Here R
+
stands for the resin cation and X

for anions like Cl

. Since uranium is one of

the few metals which can form anions in sulfuric acid solutions the exchange is very
selective, other metals such as Ca, Fe, etc., being retained in the aqueous phase as
cations.
The contact between the leach solution and the ion-exchanger may be accomplished
in different ways. Most common are perhaps fixed beds of granulated ionexchanger
through which the solution is percolated in a counter

current system. After a column
has been "loaded" it is first washed with water and then "stripped" by means of a
strong acidified chloride (or nitrate) solution. This brings the uranium back into a
relatively pure aqueous phase which is around 20 times more concentrated than the
leach solution, and regenerates the resin for a further cycle. Uranium oxide is finally
precipitated from the strip solution by neutralization.
A new concentration process similar to ion exchange has recently revolutionized the
gold industry. In this so-called carbon-in-pulp process, gold as Au(CN)
2

in low grade
leach solutions is loaded onto carbon particles, which are then separated from the
solution and stripped using a hot solution of concentrated NaOH/NaCN. Gold is
recovered from the strip solution by electrowinning. This method allows the economic
recovery of gold from solutions of much lower concentration than is possible with the
traditional approach where gold is recovered directly from solution by cementation with
zinc powder.

4.2.2 Solvent Extraction (SX)
For example, concentration of uranium and copper from low grade leach solutions.
Copper is now the most extensive application. For this purpose, organic cation
exchange liquids know under trade names like LIX 64 (LIX = Liquid Ion Exchange),
are dissolved in a carrier such as kerosene and mixed with the aqueous leach
solution. The organic liquid is immiscible with water and copper is selectively
transferred into it by cationic exchange:
2RH + Cu
2+

R
2
Cu + 2H
+

Here R represents the anionic part of the organic molecule, and Cu
2+
and H
+
represent ions in the aqueous phase. The R
2
Cu organic compound is called a
chelate. Similar exchange reactions may be written for other metal ions in the aqueous
solution such as Fe
2+
, but the equilibrium constant for the exchange is very much
lower making possible a selective separation of copper.
Introduction to Hydrometallurgy v2013 10
Once loaded with copper, the organic liquid is separated from the aqueous solution
and treated with a much smaller volume of acid to reverse the above equilibrium and
thus strip Cu
2+
into a pure and concentrated solution suitable for electrowinning.
5. Metal or Product Recovery
In this final extraction step the object is to obtain as high a purity product as possibly
while maintaining a high recovery. The product can either be a metal or some
intermediate compound which can subsequently be reduced to metal by
pyrometallurgical methods such as fused salt electrolysis. Metals are reduced from
solution by either cementation, gaseous reduction, or electrowinning while
intermediates are often recovered by hydrolysis.
5.1 Cementation
Examples are the recovery of copper from low grade leach solutions using scrap iron
and the recovery of gold from cyanide leach solutions with zinc powder:
Cu
2+
+ Fe Cu + Fe
2+
(in presence of SO
4
2

)
2Au(CN)
2

+ Zn 2Au + Zn(CN)
4
2

(in presence of Na
+
)

The product in both cases is relatively impure and must be refined by pyrometallurgy
in the case of gold and by aqueous electrorefining in the case of copper. For larger
scale copper operations, the trend is to eliminate cementation. Instead, solvent
extraction is used to give a solution which is concentrated and pure enough for
successful electrowinning. In this way it is possible to economically recover pure
copper from exceptionally low grade ores.
5.2 Gaseous Reduction
In the Sherritt Gordon Process, nickel is recovered by H
2
pressure reduction (30 atm)
at 200
o
C in an autoclave:
Ni(NH
3
)
2
2+
+ H
2
Ni + 2NH
4
+
(in presence of SO
4
2

)
In one commercial operation, copper is recovered from warmed sulfate leach solutions
by hydrogen reduction:
Cu
2+
+ H
2
Cu + 2H
+
5.3 Electrowinning
Recovery of copper and zinc is widely practiced. The metal is deposited at the
cathode with the evolution of oxygen at the inert (e.g. lead, graphite) anode. This
method is the most expensive, but gives the highest purity product.
Cu
2+
+ H
2
O Cu + 1/2O
2
+ 2H
+

Zn
2+
+ H
2
O Zn + 1/2O
2
+ 2H
+

Both are in acidic SO
4
2

solutions.
Introduction to Hydrometallurgy v2013 11
5.4 Hydrolysis/Precipitation
Al(OH)
3
is recovered in the Bayer process by cooling the leach liquor from 150
o
C to
100
o
C (precipitation):
Al(OH)
4

(aq) + Na
+
(aq) Al(OH)
3
(s) + Na
+
(aq) + OH

(aq)
In this case, cooling increases K for this precipitation reaction and dilution lowers the
concentration (= activity) of OH

in the basic solution (which lowers the pH). Both

effects favour precipitation of Al(OH)
3
.
TiO(OH)
2
is crystallized by hydrolysis of titanium sulfate (TiOSO
4
) solution in the
sulfate route for TiO
2
production from ilmenite. To enable the reaction to proceed,
steam is blown through the concentrated liquor. The resultant heating increases K for
the precipitation reaction and dilution by H
2
O lowers the H
+
concentration in the acid
solution (raises the pH). Both effects favour the formation of TiO(OH)
2
by the following
reaction:

TiO
2+
+ 2H
2
O TiO(OH)
2
(s) + 2H
+
(in presence of SO
4
2

)
The TiO(OH)
2
product is then calcined to yield TiO
2
:
The recovery stage of the Caron Process for low grade nickel ores involves the boiling
off of volatile ammonia with a resultant precipitation of Ni(OH)
2
according to:
Ni(NH
3
)
6
2+
+ 2H
2
O Ni(OH)
2
(s) + 2NH
4
+
+ 4NH
3
(g)
Since this process is done in the presence of CO
3
2

(ammonium carbonate is used in

the leach) the final product also contains nickel carbonate. However the mixed
precipitate is readily calcined to NiO.
6. Leach Regeneration and Reagent Recovery
Water in large quantities is a valuable commodity (especially in arid regions) and most
hydrometallurgical processes operate with recycled water. Thus, rather than dispose
of "spent liquor", it is passed through a leach regeneration step which aims (1) to
remove any impurities (either by precipitation or bleeding off of liquor) that build up in
the circuit and adversely affect the operation (2), to regenerate the leaching reagent if
possible (e.g.. by oxidation of Fe
2+
back to Fe
3+
when this is the oxidising agent) and
finally (3) to adjust the water balance by either making up plant losses or by removal
(distillation) of additions (e.g. when hydrolysis is used as a recovery step or wash
water is added to the circuit).
Once the water balance is correct, fresh makeup reagent is added to completely
regenerate the liquor for leaching. In some processes, the reagent is recovered
separately during the product recovery step (e.g. the distillation of NH
3
) and recycled
to make up the leach solution. The ability to recover or regenerate the leaching
reagent is an important economic aspect of process design especially when
expensive reagents such as ammonia are used. Some examples for commercial
processes are:
6.1 Bayer Process
NaOH is regenerated when Al(OH)
3
is recovered by hydrolysis. This involves cooling
and dilution of the liquor. Extra water from residue washing is also added to the circuit.
Introduction to Hydrometallurgy v2013 12
Excess water is removed by evaporation and make-up caustic added before the liquor
is recycled to the leach.
6.2 Roast/Leach/Electrowinning of Zinc
Zinc recovered by electrowinning which regenerates sulfuric acid at the anode (see
eq. for electrowinning). The sulfuric acid is recycled to the zinc oxide leach tanks.
6.3 Sherritt Gordon and Caron Processes
Nickel is stabilized in solution through complex formation with NH
3
. This volatile
reagent is removed by boiling and recycled to the leaching step.
7. Heap Leaching of Low Grade Ores
Heap leaching is an important method for treating low grade ores and can be used for,
copper sulfides (especially chalcopyrite) using Fe
3+
as oxidant in the presence of
bacteria, copper and uranium oxides using dilute H
2
SO
4
(and Fe
3+
/air in the case of
uranium) and gold ores using NaCN and air as source of oxidant.
A significant proportion of the world's copper is produced by heap leaching of low
grade oxide and sulfide ores, with the latter being bacterially assisted. Copper is
selectively extracted from the low grade solution by solvent extraction, and is then
electrowon from the concentrated strip solution, where acid is regenerated. This can
be recycled to the leaching step if electrowinning is carried out on-site. Figure 2 shows
a typical flowsheet for heap leaching of a low grade copper ore.
The leaching of copper oxide and chalcopyrite may be represented by the following
equations:
CuO + H
2
SO
4
Cu
2+
+ H
2
O + SO
4
2

CuFeS
2
+ 4Fe
3+

bacteria
Cu2+ + 6Fe
2+
+ 2S
0

Bacterial leaching is optimised by ensuring the presence of nutrients like PO
4
3

,
NO
3

, Cl

, trace elements and air. The optimum conditions for bacterial growth are pH
2 and 35
o
C but they grow and survive under a remarkably wide range of conditions.
The solvent extraction step may be represented by the following general equation:
Solvent Extraction:
2RH + Cu
2+

extract
strip


R
2
Cu + 2H
+
where R represents an organic extractant.
The electrowinning reactions are:
Cu
2+
+ 2e

Cu cathode
H
2
O + 2e

1/2O
2
+ 2H
+
anode

Introduction to Hydrometallurgy v2013 13

Impervious pad
Graded
Heap
Acid Spray / Fe
3+

STORAGE POND:
Oxidise Fe
2+
-> Fe
3+

Precipitate - basic iron
sulfate
MAKEUP ACID from
electrowinning

SOLVENT EXTRACT
Cu
2+

Drainage channels
Cu
2+

Fe
2+

Fe
2+

Fe
3+

HEAP LEACH
Concentrated & pure
Cu
2+
solution to
ELECTROWINNING Cu plus recycle acid

Figure 2

Heap Leaching of Low Grade Ores

Leach Regeneration is accomplished through aerial oxidation combined with
hydrolysis in the storage pond removing excess iron and sulfate through the
precipitation of a basic iron sulfate (Fe
3
(SO
4
)
2
(OH)
6
)
.

8. ELECTROREFINING
Although electrorefining is by far the most commercially important hydrometallurgical
refining process, its large scale use is only for the refining of copper and nickel
produced from pyrometallurgy. Copper, zinc and nickel recovered from hydro
processes by electrowinning are relatively pure and only cementation products such
as crude copper need to be electrolytically refined on a regular basis.
The principles of electrorefining have already been briefly reviewed. The process is
carried out in an electrolytic cell in which the impure metal forms the anode. This is
dissolved with the passage of an electric current and is redeposited as a pure metal on
the cathode. Impurities either enter the electrolyte or precipitate as insoluble
compounds.
These insoluble impurities or anode slimes, represent a significant source of precious
metals such as Au, Ag, Pt and Pd, since these occur along with copper and nickel in
sulfide deposits (check the periodic table!) and always report as impurities in Cu and
Ni produced by pyrometallurgy. This ability to readily concentrate virtually all of the
precious metals is a major advantage in the pyrometallurgical treatment of Ni and Cu
and is one of the reasons why pyro continues to dominate over hydro processes for
the extraction of these metals from sulfide concentrates.
9. PRACTICAL CONSIDERATIONS
From a chemical point of view, the best hydro process for a particular mineral has the
most selective leach and provides for the most selective removal of impurities.
However, a number of other practical and economic considerations also have to be
taken into account when selecting the most suitable process.
Introduction to Hydrometallurgy v2013 14
In common with pyrometallurgical processes, a hydrometallurgical flow sheet must be
designed to minimize (1) energy input (coal, oil or gas), (2) the number of process
steps to carry out extraction and recovery, removal of impurities, reagent regeneration,
and to produce a product of marketable purity and (3) the labour necessary to run the
plant. Considerations specific to hydrometallurgical processes include:
1. Ore grade and the leaching method to be employed: The grade of ore determines
whether insitu (very low grade), heap leaching (low grade), vat (higher grade) or
pressure leaching (concentrates) can economically be used.
2. Mineralogy and type of leach system: The reactivity of the mineral and gangue
towards common leaching reagents determines the leach system that can be used.
The object is to leach the mineral but not the gangue using a flow sheet that provides
for removal of impurities and regeneration of the leach solution. If significant precious
metals are present, then their recovery must be provided for.
In general, mineral reactivity depends on the class of compound and whether the
cation can form a stable complex in the leach solution. As a guide, carbonates are
more reactive than hydroxides, then oxides, and sulfides are the least reactive.
However, even minerals of the same chemical type vary widely in their reactivity. An
oxide like ilmenite (FeTiO
3)
is relatively inert towards even concentrated H
2
SO
4
(and
is pugroasted at 200
o
C) whereas copper oxide such as tenorite (CuO) will dissolve
readily in dilute acid. In some cases the gangue may be more reactive than the
mineral, e.g. dilute sulfuric acid cannot be used when MgCO
3
and CaCO
3
are present
along with CuO and NH
3
/(NH
4
)
2
CO
3
is the preferred leach.
The mineral and gangue reactivity is a useful guide, but selectivity or separation may
be achieved by controlling the thermodynamics through adjustment of temperature
and by controlling the kinetics through adjustment of temperature and time.
3. Reagent Costs: As a rule of thumb, the cost of the various sections of a mining and
processing operation can be apportioned as follows:
Mining/Processing Operation % overall cost
Mining 20
Mineral Processing 20
Extraction fixed cost Plant depreciation, infrastructure,
inventory
30
Extraction running costs Chemicals, energy, labour, waste
treatment, maintenance, sales
30

Clearly, the amount that can be spent on leaching reagents is relatively small and is
limited by the value of the metal produced and the grade of the ore. That is, more
expensive chemicals can be used for more valuable metals or for higher grade ores.
Even then, expensive chemicals can only be used if they can be recycled efficiently
with little overall loss. Within the above framework, the cost of chemicals used to
produce one tonne of metal should not exceed 10% of the metal value.
4. Equipment costs: One must also consider the cost of equipment in terms of (1) the
complexity (pressure vessels cost a lot more than open vats), (2) the materials of
construction (corrosive chemicals require expensive alloys and plastics) and (3) the
maintenance costs (more complex equipment and those handling corrosive chemicals
have higher maintenance costs).
5. Flow sheet considerations: Solid/liquid separations must be kept to a minimum
(these can be slow and expensive) and the water balance must be compatible with the
Introduction to Hydrometallurgy v2013 15
region where the plant is located (processes with large water usage are not suitable
for arid regions).
6. Waste Treatment and Tailings Disposal: Whilst hydro processes do not in general
pollute the atmosphere, great care must be taken not to pollute ground water and
effluent streams and to control discharge from tailings ponds and dumps. For
example, sulfuric acid is a relatively cheap leaching agent, but when used with
minerals containing iron, ferrous sulfate is formed and this creates a disposal problem.
It cannot be discharged into streams and therefore must either be neutralized, or
crystalized and decomposed; both are costly operations.
Basic Chemical Principles in Hydrometallurgy
Hydrometallurgical reactions occur mainly in aqueous solutions. From a
thermodynamic point of view, reactions involving ions are handled in the same way as
the solid-gas reactions already considered previously in this unit. That is, equations
can be added and subtracted as before, equilibrium constants can be calculated from
AG
o
values, and, if equilibrium is achieved, the amount of substances present can be
obtained from activity values using appropriate activity scales. We have yet to define
the activity scale for ions in solutions.
Thermodynamics can only predict what should happen and not how fast it will happen.
If the approach to equilibrium is very slow, metastable products can result rather than
those predicted from equilibrium calculations. Metastable substances are
intermediates with a prolonged life because of a slow approach to equilibrium. This
can be the case for some hydro processes since they are carried out at relatively low
temperatures. In contrast, pure processes have relatively fast reactions rates and thus,
thermodynamic calculations give a more reliable prediction of the likely outcome.
However, in both cases, thermodynamic predictions are of fundamental importance
since they establish the framework of possible reactions. Kinetic effects can rarely be
predicted and have to be established by observations.
A number of important chemical considerations applicable to an understanding of
hydrometallurgy will now be reviewed, namely: strong and weak electrolytes, activities
of ions in solution, pH of a solution, solubility products, hydrolysis, formation of
complexes, redox reactions, and electrochemical potential.
Strong and Weak Electrolytes
The large majority of substances (acids, bases, and salts) behave as so-called
electrolytes in aqueous solutions. That is, they dissociate into ions and are classified
as either strong electrolytes, when completely dissociated, or weak electrolytes, when
only partly dissociated.
A strong electrolyte, say NaCl is represented by the following equation.
NaCl Na
+
+ Cl

The single arrow indicates complete dissociation.
A weak electrolyte on the other hand, say CH
3
COOH, is represented by the following
equation:
CH
3
COOH H
+
+ CH
3
COO

The double arrow indicates partial dissociation. The extent of the dissociation in this
case is described by a constant, which depends only on the temperature of the
system.
Introduction to Hydrometallurgy v2013 16
In order to use this equation to calculate the concentrations of H
+
and CH
3
COO

, it is
necessary to relate the activities to concentration using an activity scale based on
standard or reference state. A knowledge of standard states is also essential for the
calculation of K since this is determined from the standard free energy, i.e. the free
energy difference between products and reactants of the dissociation when all are in
their defined standard states, where AG
o
= RT ln K.
The definition of a standard state and the resulting relationship between activity and
concentration sets a scale for activity of ions in solution. A knowledge of this scale is
essential not only for the above calculation of concentrations for weak electrolytes but
indeed for any thermodynamic calculations involving ions in solution.
Activities of Ions in Solution
The standard state for ions in solution is defines as 1 molal (m) solution of the ions in a
so-called ideal ionic solution, where 1 molal is 1 mole in 1000 g of solvent (equivalent
to 1 mole per liter or 1 molar for aqueous solutions at 25
o
C).
A scale of ion activities is defined by assigning the value 1 to the activity of the
standard or reference state. Thus, a = 1 when m = 1. A straight line joining these
points has the equation a = 0 which establishes the following activity scale for ions in
solution.
(i) For an ideal ionic solution:
a = m
This is known as Henrys Law.
(ii) For a non-ideal solution:
a = m
where is the ionic activity coefficient.
Real ionic equation solutions only obey Henrys Law for very dilute solutions. That is,
1 as m 0. In fact few solutions behave ideally at concentrations as high as m = 1,
and the standard state, which requires the solution to be ideal at m = 1, is said to be
hypothetical. Further, ionic activity coefficients, although simple in concept, are difficult
to experimentally define and measure. We need not be concerned with these
complications.
The pH of a Solution
The hydrogen ion activity of an aqueous solution is one of its most important
properties. It is conveniently expressed by its negative logarithm (base 10), which is
known as pH.
The activity coefficient for H
+
is normally taken as one (this is an approximation!) to
give the familiar expression:
pH = log [H
+
]
where [H
+
] represents the molarity of H
+
for aqueous solution.
Note that pH + pOH = 14. Therefore,
[H
+
] = 10
pH
and [OH
-
] = 10
pOH
and [H
+
] x [OH

] = 1 x 10
14

Introduction to Hydrometallurgy v2013 17
Solubility Product (K
sp
)
Since hydrometallurgy deals with the dissolution of solids and their precipitation from
solution, one equilibrium of great importance is that which establishes the maximum
solubility of ionic solids in water. For example, the maximum solubility of ferric
hydroxide in water can be represented by the following equation:
Fe(OH)
3
(s) Fe
3+
(aq) + 3OH

(aq)
The solubility product may be represented by the following equilibrium expression:
| || |
3
3
OH Fe
+
=
sp
K
The solubility product (K
sp
) is an equilibrium constant and has only one value for any
ionic solid at a given temperature. The solubility on the other hand is an equilibrium
position, which changes if there are common ions in the solutions. In all cases,
however, the product of the concentrations of the ions in solution must satisfy the
solubility product.
Example
The solubility product (K
sp
) for Fe(OH)
3
is 4 10
-38
. Estimate the solubility (in molL
-1
&
mg/L) of Fe
3+
in (a) sulfuric acid leach solution at pH 1.5 and (b) after partial
neutralisation of the solution at pH = 3.5.
Solution
(a) At pH = 1.5, pOH = 12.5 [OH-] = 10
12.5
molL
-1
. Therefore,
| || |
38
3
3
10 4 OH Fe
+
= =
sp
K
| |( )
38
3
5 . 12 3
10 4 10 1 Fe
+
=
| |
( )
|
|
.
|

\
|

+
3
5 . 12
38
3
10 1
10 4
Fe
M 1 =

+

~
~
=
3 1
1
3
1
Fe L mg 7000
L g 70
Fe mol
g 55.85
molL 1

(b) At pH = 3.5, pOH = 10.5 [OH-] = 1 10
10.5
. Therefore,
| || |
38
3
3
10 4 OH Fe
+
= =
sp
K
| |( )
38
3
5 . 10 3
10 4 10 1 Fe
+
=
Introduction to Hydrometallurgy v2013 18
| |
( )
|
|
.
|

\
|

+
3
5 . 10
38
3
10 1
10 4
Fe
M
6
10 1

=

+
+
+

~
~
=
3 1 2
3 1 5
3
1 6
Fe L mg 10 7
Fe L g 10 7
Fe mol
85 . 55
molL 10 1
g

Formation of Complex Ions in Solution
Complex ions are soluble chemical species comprising of a metal ion surrounded by
ligands, which act as electron pair donors as shown in the following general equation:
M + nL ML
n

This allows the dissolution of an otherwise insoluble solid by reducing the
concentration of the hydrated metal ion. The equilibrium constant, known as K
stab
, is
the ratio between the activity of the complex and the activities of the reacting species
may be represented by the following general equilibrium expression:

| |
| | | |
n
n
stab
K
L M
ML
=
For example, cobalt(II) forms a solid hydroxide but adding ammonia results in the
formation of the soluble hexaamine cobalt (II) complex as shown in the following
equations:
Co
2+
(aq) + 2OH

(aq) Co(OH)
2
(s)
Co
2+
(aq) + 6NH
3
(aq) Co(NH3)
6
3+
(aq)
the K
stab
expression for the formation of the hexaamine cobalt(II) complex may be
written as
| |
| || |
6
3
3
3
6 3
NH Co
) NH ( Co
+
+
=
stab
K

Example 1
Calculate the solubility (in molL
-1
and gL
-1
) of AgCl in (1) a hypersaline water
containing 4.0 M Cl

and (b) in the same hypersaline water but containing 2.0 M NH

3
.
The K
sp
for AgCl(s) is 1.6 10
-10
and K
stab
for Ag(NH
3
)
2
+
is 1 10
7
.
Solution
(a) The dissolution of AgCl is
AgCl(s) Ag
+
(aq) + Cl

(aq)
Introduction to Hydrometallurgy v2013 19
| | | |
| | ( )
| |
+
+

+
+
+
=
=
=

=
=
=
Ag L g 10 8 . 3
Ag mol
gL 87 . 107
L mol 10 5 . 3
L mol 10 5 . 3
0 . 4
10 6 . 1
Ag
0 . 4 Ag 10 6 . 1
Cl Ag
1 9
1
1 11
1 11
10
10
sp
K

(b) In the same hypersaline water containing 2.0 M NH
3

AgCl(s) + 2NH
3
(aq) Ag(NH
3
)
2
+
(aq) + Cl

(aq)
Let x = [Ag(NH
3
)
2
+
], 4x = [Cl

] and 2.0 2x = [NH

3
]
( ) ( )
| | | |
| |
( ) ( )
| | | |
| |
+
+

=
=
+
= =
= = =
Ag mol g 86 . 107 M 10 0 . 8
Ag M 10 0 . 8
2x - 2.0
0 . 4
10 0 . 1 10 6 . 1
NH
Cl ) Ag(NH
10 0 . 1 10 6 . 1
1 4
4
2
7 10
2
3
2 3 7 10 '
x
x x
K K K
stab sp

Exercise 1
Calculate the solubility of Co
3+
in a NH
3
/(NH
4
+
) buffer containing 0.01 M NH
3
and 0.1 M
NH
4
+
. The K
stab
for Co(NH
3
)
6
3+
is 1 x 10
34
and the K
sp
for Co(OH)
3
is 1 x 10
-43
.