HYDROMETALLURGICAL PROCESSES

Fahim Khan
Lecturer, Dept. of MSE
Khulna University of Engineering and Technology
 HYDROMETALLURGY
• Hydrometallurgy is a method for obtaining metals from
their ores.

• It is a technique within the field of extractive metallurgy.

• Involves the use of aqueous chemistry for

the recovery of metals from ores, concentrates, and
recycled or residual materials.
 OBJECTIVES OF HYDROMETALLURGICAL PROCESSING

➢ To produce a pure compound for subsequent processing to a

metal by pyrometallurgical methods. Here hydrometallurgy is
only a beneficiation step.

➢ To produce a metal from either a crude metal or a metal

compound already prepared by other methods.

➢ To produce a metal directly from an ore or a concentrate.

 STEPS INVOLVED IN PROCESSING
 Leaching: Dissolution of the desired elements from the ores in a
leaching reagent. Some preliminary preparation of ores (grinding, sizing,
physical beneficiation, roasting etc) may be necessary

 Separation of Leach Liquor: Separation of leach liquor from solid

residues (settling, thickening, filtration, etc)

 Recovery of Metal Values: Methods employed include evaporation,

distillation, precipitation, electrolysis, ion-exchange, solvent extraction,
etc.

 Recovery of Reagent: Leaching reagents are generally recycled after

purification and readjustment of composition.
ADVANTAGES OF HYDROMETALLURGY OVER PYROMETALLURGY

➢ Suited for lean and complex ores.

➢ Allows greater control over every step resulting in the recovery of

valuable by-products

➢ Reduces environmental pollution. Treatment of sulphide ores.

➢ May start on a small scale and expand later. Economic

considerations require that pyrometallurgical processes be designed
on a large scale.
ADVANTAGES OF HYDROMETALLURGY OVER PYROMETALLURGY

➢ Because of the rapidly increasing cost of metallurgical coke,

sometimes aqueous processing route is favorable.

➢ Hydrometallurgical leaching operations are generally carried out at

room or at slightly elevated temperatures. Pyrometallurgy is a high
temperature process.

➢ Deterioration of refractory lining cause periodic shutdown in

pyrometallurgy.
 DISADVANTAGES OF HYDROMETALLURGY

➢ Large volumes of solutions are to be handled for relatively smaller outputs. This
requires considerable amount of handling as well as space.

➢ Some reagents are expensive and must be recycled or regenerated for economy

➢ Reaction rates are usually slower.

➢ The disposal of effluents poses a serious environmental problem.

➢ Corrosion of tanks for storage and handling of the fluids is a problem.

Advantages often overweigh disadvantages and hydrometallurgy is becoming

increasingly important.
 THE ENERGY POINT OF VIEW
➢ Hydrometallurgical processes are carried out at room temperatures.
Apparently, therefore, pyrometallurgical processes require much more
energy.
➢ For direct treatment of low-grade ores, pyrometallurgy is inapplicable,
and therefore, there can be no comparison.
➢ For high-grade ores, pyrometallurgy requires less energy than
hydrometallurgy (per ton of metal) because of the following factors
1. Concentrated process streams
2. Accelerated reaction rates and reduced residence times
3. Exothermic nature of many reactions
 LEACHING REAGENTS
Water:
 Some compounds (CuSO4, ZnSO4) dissolve in water readily.
 Some poor grade copper sulphide ores transform slowly into water
soluble sulphate under atmospheric condition and can be
recovered by leaching.
 In commercial practice however, plain water is rarely employed as
a solvent.
Acids:
 Mineral acids (particularly H2SO4) are most common leaching
reagents
 Strong action of acids often make fine grinding unnecessary.
 During electrolysis, the acids consumed in leaching are
regenerated.
 LEACHING REAGENTS
Bases
 CHOICE OF A LEACHING REAGENT
➢ Chemical and physical character of the material to be leached.
➢ Selectivity of the leaching agent for the desired constituent to be
leached
➢ Non-corrosive to materials used in plant equipment to minimize
capital and maintenance cost
➢ Cost of the reagent
➢ Ability to be regenerated

Selectivity of the reagent toward a particular element in an ore

depends on:
 Concentration of the leaching agent
 Temperature and
 Contact time.
 LEACHING
• Leaching involves the use of aqueous solutions to extract metal from
metal bearing materials which is brought into contact with a
material containing a valuable metal

• The four basic leaching reactor configurations are in-situ, heap, vat,
agitation.
In-situ leaching Heap leaching Vat leaching Agitation leaching

• There is another type of leaching called the bacterial leaching

or bioleaching.
 LEACHING OPERATION

In-situ leaching:
(mine site, minimum use of equipment)
 leaching of the shattered rock residues left behind in the
mines
 application of leaching solutions directly to the ore-body in
the ground.
IN-SITU LEACHING: THE TECHNIQUE
 IN-SITU LEACHING: THE TECHNIQUE
➢ The leach solutions are introduced above the level of
the ore body
➢ Allowed to percolate by gravity through the ore and

➢ Collected at lower levels

➢ The pregnant leach liquor is pumped on to the

surface
➢ The technique relies on the permeability of the ore
body.
➢ Explosives are sometimes used to induce fractures
and to shatter rocks.
 DIFFICULTIES OF IN SITU LEACHING

Extreme care has to be taken to avoid loss of leach liquor to

natural ground water. This is undesirable for two counts-
 contamination of ground water

 loss of metal reducing efficiency of extraction

The technique saves the cost of mining, but has low extraction
efficiency, low extraction rates and low metal concentration in the
leach liquor.
 DUMP AND HEAP LEACHING

➢ Here the ore is arranged in a big heap

➢ Leaching reagent is continuously sprinkled over the ore

➢ Metals are extracted from the reagent that collects at the

bottom of the mountain
➢ The reagent is recycled again after metal extraction

Leaching rates can be enhanced by

Reduction of size of the ore particles

Typical extraction efficiency: 60 per cent.

DUMP AND HEAP LEACHING
 PERCOLATION LEACHING
 Leaching is carried out in a series of vats, the solution from
one vat cycling to the next.

 Theore (large enough to permit free passage of the solvent

through the voids) is loaded into large tanks.

 The tanks are then filled with leaching solution.

 Afterthe solution has been in contact with the ore for a

certain time, it is withdrawn and fresh solution is added.
 PERCOLATION LEACHING
Several stages of leaching are required
 The first leach is made with a weak (spent) solution

 The final leach is made with the strongest solution.

Thus the mineral particles which are most difficult to dissolve are
treated with the strongest solution.
 PERCOLATION LEACHING
➢ By subjecting the ore to 10 or more leach cycles, 80 – 90 per cent
of the metal values can be recovered.

➢ After the leaching cycle is complete, the ore is washed with water
and the leached ore (tailing) is removed from the leaching tank.

➢ Essentially a batch process

➢ Process most efficient for treatment of large quantities of low

grade ores.
 AGITATION LEACHING

❑ Agitationleaching involves the leaching of finely ground(200

micrometer), high grade concentrates in which the slurry or pulp is
continuously stirred to enhance the rate of leaching.

❑ This technique is also known as slime leaching.

❑ Four major types of reaction vessel used for agitation leaching are
briefly discussed in the following-
 AGITATION LEACHING
1. Pachuca Vats
❑ Stirring is achieved by the injection of
compressed air through a central vertical tube.

❑ The density of the pulp within the pipe is less

than that of the pulp surrounding it

❑ The pressure of the denser pulp causes the pulp

in the central pipe to rise and over flow.

❑ In some systems oxygen is consumed during the

reactions and this mechanism of agitation
provides the additional benefit of aeration of the
solution.
 AGITATION LEACHING

2. Low Speed Agitator:

For systems that do not require high
turbulence, large diameter paddles
or rakes may be used to mix slurries.
 AGITATION LEACHING

3. High Speed Agitators:

For leaching reactions limited
by diffusion in the leach liquor,
high turbulence may be
required. In which case the
agitator should consist of a
propeller or turbine.
 AGITATION LEACHING
4. Agitated Autoclaves:
❑ In agitated autoclaves elevated
temperatures (100-300oC) and high
pressures (up to 3.5 MNm-2) are used.
❑ High pressures are advantageous when
gaseous reagents are used
❑ The rate of leaching of gold in cyanide
solution, for example, can be increased
greatly if the pressure of oxygen over the
leaching solution is increased.
❑ The complexity and cost of such techniques
limits their application to the use of highly
concentrated minerals or high value
minerals.
BIOLEACHING
 BIOLEACHING
 Bioleaching is the extraction of metals from low-grade ores
using water, air and microorganisms, all of which are readily
found within environment.
 It is a simple and effective technology.
 WHY WE NEED BIOLEACHING?
 to reduce production costs, minimize environmental pollution,
compared to conventional leaching processes that use cyanide

 to efficiently extract metals, even when their concentration in the

ore is low.

This process is growing in popularity, as the bacteria can grow

naturally in mining environments and easily cultivated and
recycled.
PRINCIPAL COMPONENTS OF BIOLEACHING

The principal components of bioleaching all of which found

within environment are-

➢Water
➢Air
➢Microorganism
 MICROORGANISM USED IN BIOLEACHING
Bioleaching is performed mostly by iron and sulfide oxidizing bacteria, or acid
producing fungus. Some of the types of bacteria used in this process include-

Leptospirillum ferrooxidans Thiobacillus ferrooxidans

Acidianus
Sulfolobus
 CHEMISTRY OF BIOLEACHING
The reaction mechanisms are two types-
➢ Direct bacterial leaching

In this process, a physical contact exist between bacteria and ores and
oxidation of minerals takes place through enzymatically catalyzed steps
Ex; pyrite is oxidized to ferrite sulfate
2FeS2+ 7O2 +2H2O = 2FeSO4 + 2H2SO4

➢ Indirect bacterial leaching

In this process the microbes are not in direct contact with minerals, but
leaching agents are produced by these microbes which oxidize the ores.
 PROCESSES OF BIOLEACHING

There are three commercial process used in bioleaching-

✓ Slope leaching

✓ Heap leaching

✓ In situ leaching
Slope leaching
➢ Here finely powdered ore are made into large piles along the slopes of a
mountain
➢ Water containing thiobacillus is continuously sprinkled
➢ Metals are extracted from the water that collects at the bottom of the mountain
➢ The water is recycled again after metal extraction and regeneration of the
bacteria in an oxidation pool
Heap leaching
➢ Here the ore is arranged in a big heap
➢ Water containing thiobacillus is continuously sprinkled over the ore
➢ The recovery of metals and other processes are conducted just like in slope
leaching
In situ leaching
✓ Here the ore which remains in its original location in the earth.
✓ The permeability of ore is increased by sub-surface blasting
✓ Acidic water containing thiobacillus is pumped through drilled passages of the
ore
✓ The water containing ore is pumped out from the pit and the minerals are
extracted.
 EXAMPLES OF BIOLEACHING
Copper Leaching
Ores of copper from which copper metal is recovered are-

Chalcocite (Cu2S) Chalcopyrite (CuFeS2) Covellite (CuS)

Chalcopyrite contains 26% copper, 25.9% iron, 20.5% zinc and 33% sulphur.
COPPER LEACHING STEPS
➢ Generally heap leaching process is employed but sometimes a combination
of heap leaching and in situ leaching processes
➢ The solution of dilute sulphuric acid is sprinkled over the heap which
percolates through the ore
➢ The solution collecting in the bottom pit will include copper metal
➢ Which is removed by precipitation.
➢ The remaining water with Fe3+ is used again after adjusting the pH 2.0
with the help of H2SO4
COPPER LEACHING PROCESS
COPPER LEACHING REACTION
Limitation of Bioleaching
▪ The process is very slow compare to smelting and
▪ Toxic chemicals are sometimes produced in the process
 KINETICS OF LEACHING
❑ Schematic Representation of a Mineral Surface
❑ Figure below shows the two situations that can arise when a mineral
surface dissolves in a leaching reagent.
 KINETICS OF LEACHING
 When only a part of an ore body dissolves, an undissolved porous
mass is left behind.

In every situation
❑ the leaching reagent R has to diffuse from the bulk phase to the
mineral surface where there is a reaction.

❑ the soluble species containing metal M and other products P

diffuse away from the surface.
KINETICS OF LEACHING
(Complete Dissolution)
 The diffusion of the R from the bulk
of the solution to the mineral-solution
interface.
 The reaction of the reagent with the
mineral surface at the mineral-
solution interface to form a soluble
metal species.
 The diffusion of the product metal
species M (or other products P) away
from the mineral-solution interface.
 KINETICS OF LEACHING
(Incomplete Dissolution)
 The diffusion of the reagent R from the bulk of the
solution to the residue-solution interface.
 The diffusion of the reagent R through the porous
reaction product layer.
 The reaction of the reagent with the mineral
surface at the mineral-residue interface to form a
soluble metal species.
 The diffusion of product metal species M or other
reaction products P through the porous reaction
product layer in the outward direction.
 The diffusion of the product metal species M (or
other products P) away from the residue-solution
interface.
 KINETIC STEPS THAT DETERMINE THE RATE OF
LEACHING
❑ If we know the rate-determining step(s), then, appropriate
techniques required for speeding up the leaching reaction can be
adopted.

❑ If either diffusion step 1 or step 5 is rate-controlling, then rate of

leaching can be speeded up by stirring the aqueous medium.

❑ If the chemical reaction step, step 3 is rate-controlling, agitation

would have no effect.

❑ As the temperature increases, all the foregoing steps would be

accelerated.
 SELECTION OF LEACHING CONDITIONS
❖ The relative stabilities of metals and metal compounds in aqueous
solutions are conveniently represented on potential pH diagrams
❖ These diagrams indicate the predominant species that are present at
equilibrium at given reduction potentials (E) and hydrogen ion
concentrations (pH).
❖ To obtain the metal ions in solutions it may be necessary to adjust the
pH or the potential of the solutions.
❖ The pH is readily altered by the addition of acid or alkali to the
solution.

The potential of the solution may be controlled

 by the addition of chemical reagents to the solution or

 by the application of an external potential to the system.

 METHOD OF CONSTRUCTION OF POTENTIAL-PH
DIAGRAMS
❑ The first stage in the construction of the potential-pH diagram is to
identify the various soluble species that may form in a particular
system.

❑ If the mineral does not form a soluble metal species under any
conditions in one particular system, then another system is
examined.

❑ The thermodynamic data relating to the appropriate equilibrium

are determined.
Construction of Aluminum-water Potential-
pH Diagrams
 WATER STABILITY DIAGRAM
It is usual to superimpose the domain of
thermodynamic stability of water on
potential/pH diagrams by constructing lines
for the equilibria
O2 + 4H+ + 4 e = 2 H2O
2 H+ + 2 e = H2
At potentials more negative (more reducing)
than the lower boundary, water tends to
decompose with the evolution of hydrogen,
whilst at potentials more positive (more
oxidizing) than the upper boundary, water
tends to decompose with the evolution of
oxygen.
 APPLICATION OF PH-POTENTIAL DIAGRAMS

➢ Establishment of the boundaries in a

potential-pH diagram results in the
formation of domains, in each of which a
particular species is thermodynamically
stable. In domain A Zn ions are the
thermodynamically stable species. If any
other Zn species in the system is subjected
to conditions of potential and pH
corresponding to this domain, it will tend to
be converted to the Zn ionic species, i.e.,
metallic zinc and zinc oxide will tend to
dissolve.
 APPLICATION OF PH-POTENTIAL DIAGRAMS

➢ The efficiency of leaching of zinc oxide will be increased as the pH

of the solution decreases.
➢ As the potential for the dissolution of zinc is more negative than
both of the reactions determining the thermodynamic stability of
water, each of them can act as cathodic process to support the
anodic dissolution of zinc.
➢ To obtain zinc ions in solution by reaction with ZnO (s), the pH of
the solution must be lowered below 5.5.
 APPLICATION OF PH-POTENTIAL DIAGRAMS

❖ In case of Cu, equilibrium has a more

positive potential than the hydrogen
evolution reaction but it is more negative
than that of the oxygen reduction reaction.

❖ Hence Cu cannot be dissolved by means of

hydrogen evolution as the cathodic process.
❖

❖ Dissolution can only be achieved by

reduction of oxygen or some other oxidizing
agent.
 APPLICATION OF PH-POTENTIAL DIAGRAMS

❖ Gold is more noble than Cu and

the potential of the equilibrium is
more positive than even that of
the oxygen reduction reaction.
❖ In practice the metal being
unaffected by sulphuric acid and
even by strong oxidants.
 SEPARATION OF LEACH LIQUOR
Leaching of an ore results in two distinct products:
✓ A leach liquor containing the metallic values

✓ A solid residue containing the gangue.

Suspended solids are usually removed from the leach liquor by

Sedimentation
Filtration etc
When the suspended solids are removed a clear leach liquor is obtained
The leach liquor is purified of dissolved impurities
The metallic values are recovered from this purified clear solution.
PURIFICATION OF LEACH LIQUOR
PURIFICATION OF LEACH LIQUOR
The common methods of purification are
➢ Selective precipitation

➢ Ion-exchange

➢ Solvent extraction
 SELECTIVE PRECIPITATION
The impurities in the leach liquor can be eliminated through
precipitation under controlled conditions of pH, concentration, as
well as, with the help of special additives.

Traditional principles of analytical chemistry are made use in such

reactions.
✓ Iron is removed by adjusting the pH with lime or soda ash to about
3.5 and bubbling air through the solution to precipitate ferric
hydroxide without taking out other metals.

✓ Other metals, present in small amounts, are also removed at this

stage as precipitated hydroxides at appropriate pH values.
 ION-EXCHANGE

Metal ions in solutions can exchange with specific ions contained in a

solid or second liquid phase.

These reactions can provide convenient method of

❖ Removing unwanted ions from aqueous solutions

❖ Increase the concentration of selected metal ions in the solutions.

 LIQUID-SOLID ION-EXCHANGE
➢ An ion-exchange resin is a rigid framework that are chemically stable in
the solution to be treated.
➢ Groups of atoms that supply the exchangeable ions, are chemically bound
to this framework.
➢ The resins in the form of small but hard porous beads are packed in long
columns
➢ The pregnant solutions are passed through a column or a series of
columns
➢ The resin exchanges ions on its surface with ions in the solution and thus
removes them.
➢ After all the values are extracted, the waste solution is separated and
dumped. The loaded resin is acted upon by a relatively small quantity of
acid and the metal is obtained as a concentrated solution (an eluate)
➢ The resin is regenerated and is once again ready for sorption.
 ION-EXCHANGE PLANTS
➢ The resin beads are held in tall
cylindrical towers and solutions are
circulated through them.

➢ The resin beads in column A and B

are initially used for absorption,
while those in C are used for elution.

➢ When columns A and B get

sufficiently saturated with metallic
values, another change over is done.
Such change overs can be repeated
endlessly.
RECOVERY OF URANIUM FROM LEACH LIQUOR
 SOLVENT EXTRACTION
(LIQUID-LIQUID EXTRACTION)
❑ Impure compound or the ore is dissolved in a suitable acid or
alkaline aqueous medium
❑ The extractant (an organic liquid) is brought into contact with the
solution.
❑ Actual contacting is carried out by agitating the two phases
together in a vessel so as to produce a fine dispersion of one phase
in another.
❑ The two phases are allowed to separate. When quiescent, the
lighter organic phase floats on top of the aqueous phase.
❑ Metal ions enter the organic phase preferentially.
❑ The organic and aqueous layers are separated by employing
suitable techniques.
❑ The values are removed by contacting the loaded solvent
(containing the product) with another aqueous phase.
 EXAMPLE OF SOLVENT EXTRACTION

2Na4 UO2 (CO3 )3 + 6NaOH = Na2 UO7 + 6Na2 CO3 + 3H2 O

EXTRACTION OF METAL FROM THE
LEACH LIQUOR

The production of metals directly from aqueous solutions are

carried out by
❑ Reduction with another metal

❑ Chemical or gaseous reduction

❑ Electrolysis
 REDUCTION BY ANOTHER METAL (CEMENTATION)

Precipitation of a metal from aqueous solution of its salts by another

metal. Precipitation usually occurs on the surface of the added metal
and so the process is called cementation.

 When two metals are submerged in an electrolyte, while also

electrically connected, the less noble will experience galvanic
corrosion.
 The rate of corrosion is determined by the electrolyte and the
difference in nobility.
 REDUCTION BY ANOTHER METAL (CEMENTATION)

The difference can be

measured as a difference
in voltage potential: the
less noble metal is the
one with a lower (that is,
more negative) electrode
potential than the nobler
one, and will function as
the anode.
 REDUCTION BY ANOTHER METAL (CEMENTATION)

Cementation of copper is a common example. Copper ions in solution,

often from an ore leaching process, are precipitated out of solution in the
presence on solid iron.

The iron oxidizes, and the copper ions are reduced through the transfer
of electrons. The reaction is spontaneous because copper is higher on the
galvanic series than iron.
Cu2+(aq) + Fe(s) → Cu(s) + Fe2+(aq)

Iron will dissolve anodically and copper will be reduced at the cathode.

The cementation process may be regarded as a process of corrosion in

which the precipitant metal undergoes corrosion.
 REDUCTION BY ANOTHER METAL (CEMENTATION)
Several cathodic reactions are possible
O2 + 4 H + + 4e = 2H2 O
2 H + + 2e = H2
M+ + z e = M
The oxygen reduction reaction has a high positive potential in acidic
solutions, as indicated by its equilibrium on the E/pH diagrams, and
occurs preferentially to most metal ion reduction reactions when
oxygen is dissolved in solution.

As a consequence, in terms of cementation efficiency, oxygen should

be excluded as far as possible.
 REDUCTION BY ANOTHER METAL (CEMENTATION)
❑ At the early stages, the rate of metal reduction is
low.

❑ Once dissolved oxygen has been reduced and some

metal deposited, a galvanic cell is formed between
the precipitant metal and the cemented metal
deposited on it .

❑ Corrosion of the precipitant metal is then no

longer dependent upon the small differences of
potential on its surface.

❑ Virtually the whole of the exposed surface will

become anodic to the deposited metal in electrical
contact with it.