Hydrometallurgy

Agitated Leaching
Agitation may be accomplished in two ways:
Mechanical: motor-driven impellers are used. More
expensive capital and maintenance cost.
Pneumatic: compressed air or high-pressure steam is used.
This has the advantage of low initial cost and low
maintenance cost because there are no moving parts. Steam
is used instead of air when heating is desired.
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.

• 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.
 Heap/Dump Leaching
1. cover with layer of asphalt or flexible plastic sheet
2. crushed ore transport from the mine to the prepared site
by dump trucks to a level of 10-15 m high
3. The leaching agent is sprayed at the top of the dump
through which it percolates and the leach solution is
collected at the bottom.
4. When the material is fully leached, the dump is either
abandoned or re-used for leaching another batch.
In percolation leaching, ore is coarsely crushed (to 5-20 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.
Types of Leaching Reactions

In general, commercial leaching reactions can be classified into the following main types: water solvation, acid
attack, alkali attack, complexation and oxidation (often with complexation).

1. Water solvation
Water solvation refers to the dissolution of naturally soluble salts in water, such as CuSO4 or CoSO from
4 4

sulfation roasting:

These ions are actually solvated (=complexed) with water molecules and the usual convention (not followed
here for convenience) is to indicate this by Cu (aq) and SO4 (aq).

2. Acid attack
Most important examples are the dissolution of ZnO calcine (with subsequent electro winning) 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:
Oxidation
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 efficiently. Many
impurities are themselves valuable and are often recovered in separate by-product stream(s).

1. Impurity removal
Two important methods are used, namely
(i) cementation, which is based on metal displacement using the electrochemical series
(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.
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
a. Ion Exchange (IX)
For example, concentration of uranium from low grade leach solutions. Uranium is present in
acid leach solutions mainly as UO2(SO4)22 . 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:

• 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 ion-exchanger 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.
b. Solvent Extraction (SX)

1. leach solution is mixed with an immiscible organic solvent so the desired

metal ion in aqueous phase is transferred to organic phase
2. The two phases are then allowed to separate.
3. The process is then reversed by contacting the loaded organic phase with an
aqueous (strip) solution that transfers the desired metal ion back out of the
organic.
4. The aqueous phase obtained is a pure and concentrated solution suitable
for metal recovery while the stripped organic phase is suitable for recycle
Solvent Extraction
• Pregnant – loaded with the metal of interest
• Barren – metal of interest has been removed
• Pregnant aqueous – the feed solution to SX that contains the
components to be separated.
• Solutes – minor components in the feed (or other) solutions =
dissolved metals.
• Solvent – the immiscible liquid added to a process for the
purpose of extracting a solute or solutes from the feed.
• Organic – the “light” phase, used for extraction from feed.
• Raffinate – the liquid phase left from the feed after extraction =
barren aqueous.
• Strip solution – acts as the solvent to remove metal of interest
from the organic phase
Distillation for solvent recovery
 The basic requirements for
the separation of components
by distillation is that the
composition of the vapor be
different from the composition
of the liquid with which it is in
equilibrium at the boiling point
of the liquid

Distillation is concerned with

solutions where all components
are appreciably volatile , where
all liquid components will be in
the vapor phase

In evaporation , by contrast ,

of a solution of salt and water
for example , the water will
vaporize but the salt will not
3. 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.

a. Cementation
b. Gaseous Reduction
In the Sherritt Gordon Process, nickel is recovered by H2 pressure reduction (30 atm) at 200oC in an
autoclave:

Ni(NH3)22+ + H2 = Ni + 2NH4+ (in presence of SO4 2-)

In one commercial operation, copper is recovered from warmed sulfate leach solutions by hydrogen
reduction:
Cu2+ + H2 = Cu + 2H+

c. 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.

Cu2+ + H2O = Cu + ½ O2 + 2H+

Zn2+ + H2O = Zn + ½ O2 + 2H +