HYDROMETALLURGY

Introduction
• Hydrometallurgy is the name given to
chemical processing of metals in an aqueous
environment.
• There are three stages:
– The metal is dissolved from solid into an aqueous
solution.
– The solution must be purified.
– Metal must be recovered from the purified
solution as a solid.
 Leaching
• Dissolution is done by leaching.
• Leaching is a selective dissolution process.
• The unwanted components remain
undissolved.
• Separation is effected, therefore, leaching is
an extractive process.
 Solution manipulation
• The solution produced by leaching will contain
impurities and may have the wrong
concentrations.
• Methods of manipulation:
– Vacuum-enhanced evaporation: Solute concentration
can be increased by boiling under reduced pressure.
– Precipitation: Selective precipitation of the unwanted
components, or of the wanted components, for the
purpose of improving purity.
– Carrier phase: A second solvent is added to the
solution, which attracts the relevant solute. This
achieves both separation and concentration change.
 Recovery of the solute
• Precipitation: this is achieved by changing the
chemistry of the solution.
• Electro-winning: This is deposition of the
solute onto the cathode in an elctrochemical
system,
 Principles of hydrometallurgy
• Dissolution:
– Ionic nature of metals species in solution.
– Acidity, alkalinity, pH.
– Solubility, solubility product.
– Hydrolysis.
• Phase separations:
– Liquid-liquid separation.
– Liquid-solid separation.
• Countercurrent distillation.
• Clarification.
 Ionic nature of dissolved metals
• A metal in solution exists as an ionic species.
• This is a positively charged species (cation).
• The charge depends on the metal’s valency.
• Some metals can form complex ions with
other species.
• These may be anionic or cationic.
• Examples of complex ions:
– (AuCl4)- (Au(CN)2)- ((CuNH3)4)2+
 Acidity, alkalinity, pH
• Water has a tendency to dissociate into (H+) and (OH-)
ions:
H2O = H+ + OH-
• In pure water the concentration of H+ and OH- are low,
each is 10-7 moles per litre of water.
• [H+] = 10-7 and [OH-] = 10-7
• And [H+] [OH-] = 10-14
• A higher amount of H+ in the solution, i.e. [H+] > 10-7
and [OH-] < 10-7, makes the water acidic.
• The opposite makes it alkaline.
• The pH of a solution is given on a scale of 1 to 14 which
is the negative power of 10 of the concentration of H+
ions in the solution, e.g. a pH of 3 means that [H+] = 10-3
.
 Solubility
• This determines whether a metal will be easily transferred
to and from solution.
• Any solid metal-bearing compound will dissolve to some
degree in water. If only a little will dissolve, it is considered
insoluble, and since no more of it will dissolve the solution
is said to be saturated with that compound. This is the
saturation concentration of that solution.
• Equilibrium is reached when a compound is in contact with
a saturated solution.
• The saturation concentration depends on the pressure and
temperature of the system.
• For a soluble compound, a lot of the compound will
dissolve and result in a high concentration of it in the
solution before saturation concentration is achieved.
• If there is insufficient solid soluble compound in the
system, it can well all dissolve before saturation
concentration is achieved.
 Solubility product
• This is the equilibrium constant associated with
the solution.
• The compound will dissolve in the solution as
follows:
MmXn = mMx+ + nXy-
• The equilibrium constant is given by:
Ksp = [Mx+]m[Xy-]n
[MmXn]
• If there are cations/anions of the same type in
solution, less of the solid compound will be able
to dissolve.
 Hydrolysis
• Water molecules will take part in water-based
reactions.
• Some cations can react with water to form
hydroxide molecules which may be soluble or
insoluble.
• example:
(Fe3+)solution + 3H2O = [Fe(OH)3]precipitate + 3(H+)solution
 Liquid – liquid separation
• Also called solvent extraction.
• The metal is transferred from an aqueous to a
non-aqueous phase.
• The two liquids are immiscible in each other.
• The two liquids will form separate layers
(density) and can then be separated.
• The vessel used to do this is called a settler.
 Liquid – solid separation
• Leaching: The leach liquor is separated from the
undissolved solids.
• Ion exchange/carbon-based processes: A solid-state
carrier phase is employed.
• Screening: The solution is placed on a screen and the
liquid is drained (used for coarse particles).
• Filtration: The solution is placed on a filter cloth and
the liquid is forced through under vacuum.
• Countercurrent decantation: Based on sedimentation
and decantation.
• Clarification: Use of sand filters to clarify liquids.
• Solid-liquid separation is never perfectly complete.
 Countercurrent decantation
• This is done in a decantation vessel.
• The solids are allowed to settle through the
solution to form a sludge at the bottom.
• The layer of liquid above the sludge will be
essentially free from solids and can be
decanted (poured out carefully so as not to
disturb the sludge).
• A thickener is a machine that achieves
decantation on a continuous basis.
 Recovery of liquid from the sludge
• The liquid trapped in the sludge may contain the
wanted metals, and these can be lost if the sludge is
discarded.
• The sludge can be washed with water and the
sedimentation and decantation redone. The result is
that there is a lower concentration of metals in the
liquid trapped in the sludge.
• With repetition, high recovery levels can be achieved.
• The large amounts of liquid and low concentrations
produced pose a problem that can be overcome with
the countercurrent approach.
 Countercurrent approach
• The supernatant liquid from the stage is used as
the wash water in the previous stage.
• Only one addition of fresh water is required.
• In effect the wash water moves countercurrent
to the flow of solids.
• The concentration of metal in the wash water
increases from the last to the first decantation
stage.
• At the same time, the concentration of the metal
in the liquid entrained in the sludge becomes
progressively less.
Countercurrent decantation
 Clarification
• Super fine solids can make a liquid murky.
• A flitrate may contain 400ppm of fine solids.
• If the metals in solution are precipitated, the
suspended fine solids can contaminate the
precipitate and reduce the purity of the product.
• Clarification through a sand bed (filter sand):
– The liquid with suspended solids is pumped through a
sand bed in which the solids are trapped.
– The sand bed can be periodically cleaned by back-
flushing, but must also be replaced periodically.
 Clarification by filtering
• A layer of diatomaceous earth is placed on the
filter cloth.
• The solution is drawn through the layer and
cloth and the fine solids are trapped in the
diatomaceous earth.
• The diatomaceous earth layer must be
removed and washed periodically.
• Vacuum and pressure filtration are employed.
 Hopper clarifier
• A flocculant/coagulant is added to the solution to speed up the
sedimentation of the fine solids.
Leaching
 Nature of leaching
• The primary extraction process in
hydrometallurgy.
• The desired metal is transferred from the natural
minerals into aqueous solution.
• Basically, it is the selective dissolution of the
value-bearing minerals.
• The active chemical solution = leaching solution =
lixiviant.
• Examples of lixiviants: sulphuric acid,
hydrochloric acid, caustic soda, sodium cyanide.
 Nature of leaching
• Since the dissolution is selective, the unwanted
materials remain in the solid and are separated
by solid-liquid separation.
• The separated solution that contains the wanted
metals is called the pregnant solution or leach
liquor.
• The solid waste is the residue or tailings.
• The leaching is performed in a leaching vessel
before the leach liquor is separated from the
solid tailings by solid-liquid separation.
 Factors affecting the viability of
leaching
• Degree of dissolution:
– A high percentage of the value-bearing minerals must
dissolve otherwise there is a loss of metal.
• Selectivity of leaching:
– Selective leaching prevents unwanted metals from
entering the leach liquor, thus improving the purity of the
leach liquor. Impure leach liquors necessitate expensive
refining processes.
• Cost of lixiviants:
– The cost and quantity of the lixiviants needed per ton of
ore processed is important.
– Some lixviants can be recycled and reused, but the extent
to which they are progressively consumed during the
process is important. E.g. An acidic lixiviant will be
consumed by a carbonate gangue.
 Leaching thermodynamics
• The leaching reaction is:
[MA]solid = (M+)aqueous + (A-) aqueous
• The solubility of MA in the lixiviant must be
high and the concentration of MA in the solid
phase must be small when equilibrium is
reach with the lixiviant.
• For selectivity, the solubility of unwanted
solids must be low.
 Leaching kinetics
• Only the surface of the mineral is exposed to the
lixiviant.
• Dissolution starts from the surface inwards and
so is slow.
• Dissolution at the surface may be slow because:
– Diffusion rates of the reagent in the solution are slow.
– Rate of chemical reaction is slow.
– Diffusion of reaction product away from the reaction
site is slow.
– The remaining solid, which must be porous, may
impede the progress of the reaction.
 Factors affecting kinetics
• Particle size:
– The finer the particle size the greater the total surface area of
mineral exposed to the lixiviant.
– Complete liberation is not necessary, as long as some part of the
mineral is exposed to the lixiviant.
• Diffusion rates:
– Diffusion of reactants to, and products from the solid’s surface
controls the reaction rate.
– Agitation can increase diffusion rates in the liquid.
– Agitation does not improve diffusion through porous solid. For
this, increase in porosity, temperature, and reagent
concentrations are necessary.
• Chemical reaction rates:
– These can be increased by: Increased surface area of solids
(finer grind), increased temperature, increased/decreased
pressure, addition of catalysts.
 Leaching curve
• Leaching kinetics can be
assessed by dissolving
the minerals in the
lixiviant over a period of
time, taking periodic
measurements of the
concentration of the
metals in solution.
• The factors affecting the
kinetics will change the
shape of the graph.
Types of leaching reactions
 Dissolution of metal salt
• Some metal salts (e.g. KCl, Na3VO 4, and some
metal suphates and chlorides) are soluble in
water.
• Eg. [CuSO4]solid = (Cu2+)aqueous + (SO42-) aqueous
• Most minerals are not soluble in the their
natural states, but can be rendered soluble by
pyrometallurgical pre-treatments, such as
sulphatising and chloridising.
 Acid dissolution
• Many compounds, especially oxides, are
soluble in acids.
• Sulphuric acid is the most used acid lixiviant.
• The metals occur as simple or complex cations
in solution.
• Examples:
[ZnO]solid +2(H+)aq = (Zn2+)aq + H2O
[UO3]solid +2(H+)aq = (UO22+)aq + H2O
 Alkali dissolution
• Some metal form water-soluble complex
anions in alkaline solutions.
• Example:
[Al2O3]solid + 2(OH-)aq = 2(AlO2-)aq + H2O
 Anion exchange
• Part of the mineral is dissolved and another part
reacts with an ion in the lixiviant to form a new
solid compound.
• Example:
[CaWO4]solid + (CO32-)aq = [CaCO3]precipitate + (WO42-)aq
• There is an exchange of anion between the solid
and the liquid.
 Formation of complex ions
• Leaching can be more feasible if the metals
becomes part of a complex ion.
• Examples:
2[Au] + 4(CN-) + H2O + ½{O2} = 2(Au(CN)2-) aq
[CuO] + 2(NH4+) = (Cu(NH3)2+)aq + H2O
• The solubility of weakly soluble salts is
increased this way.
• Dissolution may be achieved at pH levels
where solubility would otherwise by
negligible.
 Redox reactions
• In reduction-oxidation reactions, one
component is oxidised while the other is
reduced.
• Examples:

[ZnS] + 2(Fe3+) = (Zn2+) + 2(Fe2+) + [S]

[MnO2] + 2(Fe2+) + 4(H+) = (Mn2+) + 2Fe3+ + 2H2O

Bacterial Leaching
 Organisms used in bacterial leaching
• The micro-organisms used belong to the Thiobacillus
family, the most common species used being:
Thiobacillus ferrooxidans, which has the following
properties:
– It is a rod-shaped bacterium (1μ by 0.25μ).
– It is aerobic (needs O2 to live).
– Thrives in acidic conditions (optimum pH = 2.5).
– Optimum temperature is 25° to 35°C.
– Can flourish in solutions with high concentrations of metal
ions.
– Can propel its self in solution.
– Reproduction by cell division every 10 hours.
 Bacterial leaching reactions
• The organism use the energy released by the
reactions for survival.
• The reactions are mostly basically the same as
the chemical reactions used in leaching, but
the bacteria increase the reaction rates. Also,
different reactions can take place.
• The most important is the conversion of
sulphides into sulphates.
 Oxidation of ferrous to ferric ions and
then oxidation by ferric ions
• Pyrite or pyrrhotite are used to make ferric ions:
• FeS2 + ½O2 + H2O (with bacteria) = FeSO4 + H2SO4
• FeSO4 + H2SO4 + ½O2 (with bacteria) = (Fe2SO4)3 + H2O
• The Ferric ion (Fe2SO4)3 is used to oxidise pyrite or
bivalent metal sulphides such as ZnS, Ni2S3, and CuS.
• FeS2 + (Fe2SO4)3 = 3FeSO4 + 2S
• MS + (Fe2SO4)3 = 2FeSO4 + MSO4 +S
 Direct oxidation
• Theobacillus ferrooxidans can oxidise metals
directly.
• Here the bacterium is not only increasing a
normal reaction, it the agent of the reaction.
MS + 2O2 (with bacteria) = MSO4
 Dissolution of oxides
• The organism can produce sulphuric acid
directly by the oxidation of elemental sulphur
S + H2O + O2 (with bacteria) = H2SO4
• The production of sulphuric acid is also a
byproduct in other oxidation reactions.
• The sulphuric acid also helps in the dissolution
of the oxide minerals.
Types of leaching systems
 Agitated leaching
• Performed in a vessel called a contactor.
• The solid and lixiviant are mixed to form a
slurry.
• The solids are in a fine particulate state to
ensure a high degree of exposure to the
lixiviant.
• Continuous agitation is necessary.
• A maximum degree of contact between solid
and lixiviant can be achieved.
 Agitated leaching
• The contactor may be flat or conical bottomed.
• Agitation can be achieved mechanically or
pneumatically.
• The process can be a batch process in which the
contactor is charged with solids and lixiviant that
are agitated for a period of time and then
removed, before the next batch operation is
performed.
• Continuous process systems are also used, where
there is co-current flow of solids and lixiviant feed
through at least three contactors.
 Leaching without agitation
• Good contact between lixiviant and solids can be
achieved without agitation.
• This can be done by immersing the solids into the
lixiviant, or by allowing the lixiviant to percolate
through a bed of the solids.
• Advantages:
– The equipment is simpler and cheaper.
– Solids do not need to be crushed.
– The lixiviant passes through the bed of solids and
separation is automatically achieved without applying
solid-liquid separation processes.
 In situ leaching
• Also known as solution mining.
• Lixiviant is pumped directly into the ore body
in the ground.
• The porosity of the ore may have to be
artificially increased by blasting.
• The process has low efficiency.
• Leaching times are long, and can extend for 20
years before the ore body is depleted.
 Dump/heap leaching
• The solids are piled up and lixiviant is sprinkeled over them.
• The solids are usually coarse grained and of low grade.
• The lixiviant percolates through the pile and accumulates in
a pond beneath (pregnant solution).
• After recovery of the metal from the pregnant solution, the
lixiviant can be recycled for further leaching.
• Long leaching times and low levels of recovery are
expected.
• Where the piles of solids are dumps of previously treated
materials, the process is called dump leaching.
• The base of the heap must be specially prepared so the
pregnant solution is not lost into the ground. This may be
done a concrete slab or layer of bentonite clay.
 Vat/percolation leaching
• The solid material is crushed to the required size
and laid as a bed in a tank/vat.
• The lixiviant is added from above and allowed to
percolated through the bed.
• The solution can be recycled continuously causing
the concentration of the metal in the solution to
gradually increase.
• One the leaching is complete, the vats/tanks are
emptied and the solids discarded.
• No solid-liquid separation is needed because the
grain size is too fine.
 Counter current decantation
• The main aim of counter current decantation
is to separate very fine solids from the
pregnant solution.
• During the process, leaching takes place.
 High temperature leaching
• Temperature affects both the thermodynamics and
kinetics of reactions.
• Normally, an increase in temperature will promote
leaching.
• In most situations, an increase in temperature of a
large volume of lixiviant is not economical, and so is
used only where the leaching is not feasible at ambient
temperatures.
• Heat can be applied electrically or by the injection of
steam. Alternatively, the lixiviant can be first heated up
by a heat exchanger before entering the contactor.
• Added insulation, vapour control and safety measures
are necessary where heat is applied.
 Pressure leaching
• Pressure can have an effect on the leaching
process, especially if the reaction involves a
gaseous component.
• The pressure of a system can be elevated by
increasing the temperature above the boiling
point.
• The pressure can also be increased by
pressurisation in an autoclave.
• The vessel must be fully enclosed and capable of
withstanding the pressure.
• The particles need to be very fine-grained.
Precipitation
 Purposes of precipitation
• To refine a metal-bearing solution: Where the
pregnant solution contains impurities, these can be
selectively precipitated until the necessary purity of
the liquor is achieved.
• To increase the metal concentration of the
solution: Precipitation of the metal from a large
volume of solution and re-dissolving it in a smaller
volume.
• To recover a metal from solution:
Sometimes, elemental metal can be precipitated from
solution.
 Precipitation and crystallisation
• Precipitation occurs when a dissolved species
exceeds its solubility limit (saturation) and
exsolves as a solid.
• The term crystallisation is used when the
solids that exsolve are coarse (large) granular
particles.
 Supersaturation
• When the solute’s concentration in solution
exceeds its saturation solubility, the solution is
said to be supersaturated.
• This situation is unstable and occurs only where
the kinetics have prevented precipitation.
• Supersaturation can be achieved by; Cooling,
heating, evaporation, addition of salt or solvent,
or by adding a reagent.
• The degree of supersaturation drives
precipitation. The higher the concentration of
the solute the greater the tendency to
precipitate.
 Nucleation and crystal growth
• Nucleation is the process of dissolved species
becoming solids.
• Crystal growth occurs when dissolved species
nucleate onto existing solids.
• Crystal growth follows nucleation as more of
the dissolved species attach themselves to
the crystal lattice.
• Precipitation consists of nucleation followed
by crystal growth.
 Types of nucleation
• Homogeneous nucleation: Clusters of solute
molecules are formed. When they reach a critical
size a lattice forms which is the nucleus for
further crystal growth.
• Heterogeneous nucleation: The process is the
same as homogeneous nucleation, but it is
catalysed by foreign objects and the vessel walls.
• Secondary nucleation: Crystals can be added as
seeds to initiate nucleation and crystal growth.
 Requirements for precipitation to
occur
• A significant degree of supersaturation is needed.
• The degree of supersaturation can be visualised
on a solubility diagram.
• There are three regions on the diagram.
– The stable region is low levels of saturation where no
precipitation will occur.
– In the metastable region precipitation will occur if
there a re seed crystals.
– Spontaneous precipitation will occur in the liable
region and will continue until the saturation levels fall
below the metastable region.
Solubility diagram
 Control of the crystallisation process
• It is better to promote the crystallisation of large
crystals rather than the nulceation of many small
nulcei. This is because fewer larger grains are
easier to handle and separate from the liquid that
many tiny ones.
• If a solution becomes supersaturated rapidly,
nucleation is favoured and many tiny nuclei form.
• If a solution becomes supersaturated slowly,
crystal growth is favoured so larger crystals form
from few nuclei.
Methods to induce super-saturation
 Changes in concentration
• The concentration of a solute can be increased
by evaporation of the solvent (i.e. boiling).
• Example: ammonium paratungstate is
precipitated from a solution containing
ammonium tungstate by evaporation.
 Changes in temperature
• Solubility generally increases with increasing
temperature, so it can be decreased by
decreasing temperature.
• However, not all solutions become saturated
when the temperature is decreased. A change in
the solute molecule (phase change) can alter the
solubility pattern.
• Another danger is the precipitation at low
temperatures of co-dissolved species that can
form scale on the precipitation vessels.
 Addition of a chemical reagent
• Dissolved species react with the added
reagents to for insoluble compounds.
• Examples:
– Precipitation of metal hydroxides by increasing the
pH (e.g. NaOH).
– Precipitation of metal suphides by the addition of
H2S gas to a solution containing metal sulphates.
 Addition of a second solute
• Addition of a new solute with very high
solubility to the solution causes the solubility
of the existing solute to decrease, causing it to
precipitate.
• Examples:
– Precipitation of nickel chloride by the addition of
HCl.
– Precipitation of Calcium hypochlorite by the
addition of NaCl.
 Precipitation of metal
• Cementation: Adding a highly soluble (less noble)
metal as a second solute, can cause the dissolved
metal to precipitate as a finely divided metal.
• Example: (Cu2+) + [Fe] = [Cu] + (Fe2+).
• Cementation is often used to scavenge Cu from
discard solution, to extract Au (using Zn), and to
purify zinc electrolytes.
• Gaseous reduction: Addition of a reducing gas
(e.g. H2) causes precipitation of metal.
• Example: (Ni2+) + {H2} = [Ni] + 2(H+)
 Precipitation processes
• Precipitation is done in precipitors which are
agitated tanks with temperature control.
• Feed solution and reagents are added to the
tanks and the precipitate slurry needs to be
removed.
• Recovery of the precipitated solids involves solid-
liquid separation by way of thickening followed
by filtering.
• Agitation is needed to prevent areas of excessive
super-saturation.
• Control of the super-saturation rates is needed to
control the resulting particle sizes.
Control of the precipitation conditions
• The temperature and concentration under which
super-saturation occurs needs to be carefully
controlled.
• Cooling can be achieved by passing water
through coils submerged in the solution.
• Agitation is needed to prevent a buildup of
precipitate on the coils which will affect heat
transfer.
• Too much agitation can promote further
nucleation and reduced crystal size.
 Bayer process
• Used in the production of pure Alumina from
Bauxite.
• Alumina is dissolved from bauxite using caustic
soda.
• The clarified leach liquor contains sodium
aluminate.
• Aluminium trihydrate is precipitated from the leach
liquor by cooling and the addition of seed crystals.
• The crystals are passed through hydrocyclones. The
oversize fraction (>100μm) dewatered, washed,
dried and calcined to produce Al2O3 (alumina).
• The undersize fraction is used as seed for
precipitation.
 Production of electrolytic zinc
• Zinc oxide calcine is dissolved in sulphuric acid.
• The aim is to recover the Zn by electrolysis.
• Co-dissolution of iron as an impurity takes place.
• The leach liquor is filtered and heated.
• Lime is added to the hot solution to cause the
iron to precipitate as Fe2O3.
• The Fe2O3 can easily be removed by filtration.
• However, gelatinous ferric hydroxide can also be
precipitated and it is difficult to separate. To
prevent this, agitation is needed to prevent areas
of high pH , which promotes the precipitation of
gelatinous ferric hydroxide .
 Processes that use a carrier phase
• Non-aqueous carrier phases are mediums used to
transfer the metal from one solution to another.
• Carrier phases include:
– Ion-exchange resins.
– Solvent extractants.
– Activated carbon.
• The metal is transferred from the aqueous
solution to the carrier phase, from which it can
then be eluted (transferred into another
solution).
Advantages of using carrier phases
• Concentration of a dilute solution by evaporation
involves boiling off of large amounts of water which is
costly.
• Precipitation from a dilute solution (under saturated) is
also costly and difficult.
• Low concentrations do not affect recovery of metal by
ion-exchange or solvation, it just takes a little longer.
• Liquid-liquid separation (during solvation) of liquids
with different densities is easy.
• Solid-liquid separation of coarse-grained resin or
carbon granules is easily done by screening, unlike the
filtration needed for fine-grained precipitates.
 In-pulp process
• This method eliminates the need for difficult
separation of fine solids from the leach liquor.
• The carrier phase (granules of resin/carbon) is
simply added to the un-clarified pulp (mixture of
solids and liquor).
• The metal is transferred from the pulp into the
carrier phase.
• The pulp and carrier phase (coarse-grained) are
then separated by screening.
• The metal can then be eluted from the carrier
phase.
 Purposes of carrier phase processes
• Concentration: Metal is transferred from a dilute
solution to a concentrated one via a carrier
phase.
• Refining: Selective transfer of metals from one
solution to another producing a purer solution.
• Extraction: To recover metals from low
concentrate solutions that would otherwise be
discarded (i.e. scavenging).
• In-pulp process: To avoid the need for filtering
and clarification.
Metals treated using carrier phases
Processing Metals processed
technique
Ion exchange U, Cu, Au

Solvent extraction U, Cu, Ni, Co, Zn, Mo, W,

V, REE, PGMs, Zr, Hf
Activated carbon Au, Ag, Mo
Stages in the processes
that use a
carrier phase
 Loading or adsorption stage
• Extraction of the metal from solution and its
transfer to a carrier phase.
• The carrier phase becomes “loaded” with the
metal.
• The metals are adsorbed onto the carrier
phase.
• Intimate contact between the liquor and the
carrier phase is essential from high recovery of
metal.
 Separation of loaded carrier and
barren solution
• If the carrier phase is solid it is separated from
the liquid by screening. The carrier phase is
always designed to be coarse-grained so that
filtration is unnecessary.
• If the carrier phase is liquid, it is immiscible
with the liquor. Once the liquids form two
layers they can be separated.
 Stripping or elution stage
• The metals contained in the loaded carrier are
recovered by introducing a different solution that
re-dissolves the metal. This is called stripping or
elution.
• The new metal-bearing solution is called the
eluent.
• The volume of the eluent is much less than that
of the original leach liquor.
• Elution is done repeatedly to ensure that most of
the metal is recovered.
• The eluent is separated from carrier phase by
screening.
 Regeneration of the carrier phase
• The carrier phase can be reused after elution.
• The amount and type of treatment needed to
regenerate the carrier phase for reuse
depends on the type of carrier phase and the
type of contaminants on it.
 Adsorption and stripping cycles
• Recycling the carrier phase is necessary for
economic reasons.
• The cycle of the process is:
1. Loading of the carrier phase (adsorption cycle)
2. Stripping of the carrier phase (elution cycle)
3. Regeneration of the carrier phase.
• The process can be a batch, semi-continuous
or continuous operation.
• Solvent extraction is a continuous operation with
the carrier phase flowing from the adsorption
vessels into the elution vessels and then back
again.
• Solid carrier processes are semi-continuous. Here
the feed solution flows continuously through the
adsorption vessels, but the carrier is added and
removed in batches. Each batch is added for the
duration needed to acquire a full load.
 Properties of carrier phases
• Adsorption properties: The carrier must have a high,
but selective affinity for the target metal.
• Desorption properties: The metals must be
recoverable by elution from the carrier.
• Separability: Easy separation of the carrier phase from
the aqueous solution is necessary.
• Re-usability: For economical reasons, the carrier must
be re-usable with minimum regenerative treatment.
• Durability: The carrier must withstand continual reuse
without deterioration of its physical and adsorption
properties.
 Ion-exchange resins
• Synthetic materials designed for adsorbing
metals.
• They are made from macromolecular , insoluble
polymers (polystyrene), and are porous.
• The are made into small beads, 0.3-1.2mm in
diameter.
• They are hard, durable and easily screened, so
they can be recycled repeatedly.
• The polymeric material has excess electric
charges on its surface, onto which oppositely
charged ions (counter-ions) can attach.
• There are two types of ion-exchange resins:
– Anion exchangers: Have positive charged
framework and can exchange anions.
– Cation exchangers: Have negative charged
frameworks and can exchange cations.
• An anion exchangers will have counter-anions.
• When the resin is immersed in the liquor, the
metal ions will enter the resin pores and
replace the ions while the counter-ions will
float out. The resin maintains electrical
neutrality through the ion exchange process.
 Selectivity of ion-exchangers
• Ion-exchangers are very selective.
• Example:
UO2(SO4)22- > UO2(SO4)22- > HSO4- > Fe(SO4)2- > SO22- > Cl-
• The affinity of UO2(SO4)22- is much greater than HSO4-, so it
can be selectively adsorbed from a sulphuric acid solution.
• Elution is the opposite of loading.
• In the loading cycle, metal ions replace the counter ion in
the resin, and in elution counter ions replace metal ions in
the resin.
• The resin has a finite number of charged sites to which the
ions can adsorb. This is the ion-exchange capacity.
Loading and elution cycles
Distributi on
Coefficien ts :
[ A]rex
DA 
[ A]sol
[ M ]res
DM 
[ M ]sol
Equilibriu m :
[ M ]res [ A]sol
Q 
M
A
[ A]res [ M ]sol
Loading :
( R  A ) res  ( M  ) sol  ( R  M  ) res  ( A ) sol
Elution :
( R  M  ) res  ( A ) eluent  ( R  A ) res  ( M  ) eluate
 Solvent extractants
• These are organic solvents that are immiscible in
aqueous solutions.
• The organic solvents are hydrocarbon chains with
attached functional groups that are similar to those in
resins.
• Solvents extract metals from solution by dissolution or
ion-exchange.
• Non-ionic species will simply dissolve in an organic
solvent.
• Some solvents react with metals to form organo-
metallic complexes that are soluble in organic solvents.
This is called chelating.
 Activated carbon
• A highly porous solid material in the form of granules
0.5-3mm in size.
• Manufactured from carbonaceous material such as
coal, wood or coconut shells.
• The carbonaeous material is charred (burnt under
reduced oxygen conditions) to carbonise it.
• The carbonised material is activated by selective
burning to produce a highly porous material with a
large internal surface area of about 1000m2/g, and a
pore volume of about 0.8cm3/g.
• Activated carbon has no affinity for small highly
charged ions.
 Elution of loaded carbon
• Stripping loaded carbon is different from the
adsorption reactions.
• Example: Au extraction:
– Au is adsorbed onto carbon from dilute cyanide
solution at pH 8.5-12.
– For desorption, the carbon is soaked in hot caustic
cyanide solution and eluted by hot de-mineralised
water.
 Regeneration of carbon
• Carbon looses some of its adsorptive properties
after contact with solution.
• Regeneration is needed to restore these
properties.
• The carbon is regenerated by heating in a rotary
kiln at 700-900°C in a steam atmosphere.
• Carbon may be acid washed to remove carbonate
scale that may have accumulated on it. This can
be done before or after regeneration.
 Ion-exchange columns
• The ion-exchange column is a cylindrical steel vessel that is lined
with rubber.
• The resin beads are inserted and form a bed over a perforated
base.
• The solution is pumped through, either upwards or downwards.
• Metal exchange starts from the inlet side of the column as soon
as the solution contacts the resin. The resin becomes saturated
progressively from the inlet side of the column. Barren solution
exits from the other side of the column. When all the resin in the
column is saturated, metal-bearing solution will exit the column
– this is called breakthrough. The process needs to be stopped
before breakthrough is reached, otherwise metal-bearing
solution will exit the column.
• The process is stopped just before breakthrough, and then
stripping solution is pumped through to elute the resin and
recover the metal.
 Moving-bed ion-exchangers
• The normal ion-exchange column is a fixed-bed system, and is
semi-continuous in that loading and stripping cycles occur
sequentially. Often a number of columns are employed so that
while one is in the loading cycle another is in the stripping cycle.
• A moving-bed system aims to achieve a continuous flow
operation.
• The column is separated into compartments by perforated
plates.
• Upwards flow keeps the beads in suspension preventing them
from dropping into lower compartments.
• By adjusting the flow rate, the beads can be transferred into
lower compartments (counter current) and be progressively
removed from the bottom.
• The loaded resin is stripped in a separate vessel. It can then be
regenerated and reused.
 Resin-in-pulp and resin-in-leach
• Where the solution that is used in ion-
exchange is not clarified leach liquor, but un-
separated pulp, the process is called resin-in-
pulp ion-exchange.
• Resin can also be added to the pulp in the
leaching vessels, so that leaching and
adsorption take place at the same time. This is
called resin-in-leach.
 Carbon-in-pulp processes
• Activated carbon can adsorb up to 30% its weight of Au and
Ag, so small amounts of it are needed for extraction.
• Loading vessels are tanks with mechanical agitation
facilities, so that the pulp and carbon remain in suspension.
• Loading of the carbon takes place in the tanks. The slurry
flows from one tank to the other so that all its metal can be
adsorbed.
• The carbon granules are periodically pumped counter
current to the slurry flow form one tank to the other and
ultimately to an elution tank.
• The metal is finally recovered from the eluate (metal-
bearing).
• The carbon is separated from the eluate by screening and
regenerated before being reused in the loading vessels.
 Carbon-in-leach processes
• Carbon is added to the leaching tanks and metal is
simultaneously leached from the ore and adsorbed
onto the carbon.
• This has the following advantages:
– Fewer tanks are needed since two operations are
performed in one tank.
– Constant removal of metal from the leach liquor improved
the reaction kinetics of the leaching stage.
• Disadvantage:
– Leaching of Au required high concentrations of cyanide,
but high concentrations of cyanide prevent the adsorption
of Au onto carbon.
 Solvent extraction: loading step
• The metal is transferred into an organic solvent (liquid)
rather than a solid.
• The metal is transferred across the interface of two
liquid phases.
• This requires a very large interfacial surface area, which
is achieved by vigorous mixing to form a suspension of
tiny droplets.
• If the organic liquid is the larger volume of the two, the
system is called organic continuous. Alternatively, it is
called the aqueous continuous.
• Transfer kinetics is rapid.
• The result is a loaded organic phase and a barren
aqueous phase (called a raffinate).
Solvent extraction: Separation step
• The loaded organic phase and raffinate are separated
in a vessel called a settler.
• The intimately mixed fine droplets must disengage by
being allowed to quiet down. The droplets will then
either sink or float depending on their densities.
• The rate of disengagement depends on the sizes of the
droplets, the interfacial tension and the density
difference.
• Sometimes a stable emulsion is formed called a crud.
This is a mixture of the two liquids. It normally forms at
the boundary between the two layers of liquids.
• If loaded organic liquid is entrained in the raffinate, a
loss of values will result.
Solvent extraction: Stripping stage
• The process is the sames as that of loading,
except that the metal is now transferred from
the organic phase into a different aqueous
phase.
• The new aqueous solution has a much smaller
volume than the original, i.e. a much higher
concentration.
 Solvent extraction: Equipment
• The loading takes place in vessels where agitation can be
performed, called mixers.
• Separation takes place in quiescent vessels called settlers.
• These tow functions can be combined into one piece of
equipment called a mixer-settler.
• This vessel has two compartments. Loading takes place in
the one where there is agitation. The overflow enters a
quiet compartment where separation occurs. The aqueous
liquid exits by an underflow stream and the organic phase
by a overflow outlet.
• A train of these vessels can be employed to take advantage
of repeated loading.
• Also, loading and stripping cycles can be arranged in one
train of vessels.
Hydrometallurgical circuits
 Extraction of gold: Leaching
• Gold usually occurs as tiny particles in the
rock. Sometimes it is enclosed in other
minerals.
• The rock is milled to liberate the gold
particles.
• The mill slurry is thickened to a 1:1 water:solid
ratio.
• Lime is added to raise the pH of the slurry to
9-12.
 Extraction of gold: Leaching
• The thickened slurry is pumped into a series of
leaching tanks.
• Cyanide is added to the first tank of the series
in a concentration of 150ppm.
• Air is injected so that O2 is present during the
leaching.
• Leach times of at least 48 hours are needed.
• 2[Au] +4(CN-) +H2O +½O2 = 2Au(CN)2- + 2(OH)-
 Extraction of gold: Cementation
• The leach slurry is filtered by drum filters.
• The filter cake is washed to recover entrained gold-bearing solution.
• The washing causes the concentration of Au in the solution to drop to 2-5ppm.
• The filtrate is clarified to ensure that there are no fine solids to inhibit the
precipitation and contaminate the precipitate.
• The filtrate is also de-aerated to prevent the oxidation of the Zn which will be
added to the solution.
• Zn dust is added to the solution (with lead salt) which causes the Au to
precipitate.
• The solution is thoroughly mixed in a precipitation vessel and forced through a
pre-coated filter medium.
• The Au precipitate is treated with acid to remove soluble base metals and
residual Zn.
• It is then de-watered and calcined at 650°C to oxidise the remaining base
metals.
• The metal is then smelted and the oxidised base metals enter the slag, and the
metal (molten gold bullion) is cast into bars.
 Extraction of tungsten: Leaching
• The main ore minerals that contain tungsten are scheelite
(CaWO4) and wolframite ((FeMn)WO4).
• The ore have grades of ±0.4% WO3, but are enriched to 20-70%
by gravity concentration.
• Scheelite is normally associated with other minerals such as
apatite (Ca5(PO4)3), as well as sulphide and arsenide minerals.
• These other minerals are removed by leaching the concentrate
in HCl. If the contents of sulphur and arsenic are high, the
concentrate is first roasted at 600-800°C.
• The Tungsten is extracted using a 10-18% sodium carbonate
solution at 190-225°C and 12-26atm pressure in an autoclave.
• The reaction takes 1.5 – 4.0 hours.
• (Na2CO3)+ [CaWO4] = (Na2WO4) +[CaCO3]
• The leach solids are separated by filtration.
Extraction of tungsten: Purification
• The NaWO4 solution is generally contaminated with
silica, phosphorus, arsenic, and molybdenum.
• Silica must be below 2g/litre. Ideally 0.06g/litre.
• It is removed by precipitation as sodium alumino-
silicate or magnesium silicate.
• To do this, Al2(SO4)3.18H2O (alum) and MgSO4.7H2O
(magnesium sulphate) are stirred into the solution at a
pH of 9.0-9.5 and temperature of 70-80°C for about an
hour. The precipitate is filtered out.
• Much of the phosphorus is removed during the
removal of silica.
Extraction of tungsten: Purification
• Removal of molybdenum is done by forming
thiomolybdenate ions and then converting them
to molybdenum trisulphide.
• MoO42- + 4S2- + 4H2O = MoS42- + 8OH-
• MoS42- +2H+ =[MoS3] +{H2S}
• Enough acid is added to reduce the pH to 2.5-3.0
at a temperature of ±80°C. After 7-8 hours the
MoS3 is precipitated and removed by filtration.
• The resulting purified solution has a pH of 2.5 and
a temperature of 40-55°C.
 Extraction of tungsten: crystallisation
• Tungsten is recovered from solution in the form of ammonium
paratungstate (APT) via solvent extraction.
• The solvent is Alamine 336, which is a macromolecular hydrocarbon
with an amine group dissolved in kerosene.
• The solvent and aqueous solution are thoroughly mixed and ~99%
of the tungsten can be transferred.
• After separation, the solvent is washed with de-ionised water to
remove all entrained aqueous solution and sodium.
• The solvent is stripped by aqueous ammonium solution at 60°C.
• The recovered APT crystallises and is recovered by vacuum-
enhanced evaporation.
• The APT crystals are washed, steam dried and calcined to oxide.
• The oxide can be reduced to pure metal by using H2 gas at 1000°C,
or to tungsten-carbide by the use of carbon.