The Copperbelt University

School of Mines and Mineral Sciences

Zambia.
Chemical Engineering Department

Pyro-Electro &
Hydrometallurgy
By
Evans Chomba
evans.chomba@cbu.ac.zm
Content
 Chemical Processing

 Hydrometallurgy
– Basic Circuits
– Leaching
– Solvent Extraction
– Precipitation

 Pyrometallurgy
– Smelting

 Electrometallurgy
– Electrowinning
Chemical processing
 Hydro- Versus Pyrometallurgy:
 Techniques have competed over the years

 Pyrometallurgy:
– Very ancient technology
– was most successful with high-grade, simple ores, large scale
– High temperature, fast reaction
– Problems can include pollution of the environment, high energy
consumption, and excessive dust formation

 Hydrometallurgy:
– works better with low grade, complex ores, smaller scale
– Lower temperature, slower reaction
– First hydrometallurgical process: alumina from bauxite, at start of 20 th
century
Terminology
 Hydrometallurgy: aqueous
methods of extracting metals
from their ores
 hydrometallurgical plant: large
amounts of water are needed,
and a water balance must be
maintained
 Generally involves two distinct
steps:
 leaching = Selective dissolution
of the metal values from an ore
 precipitation = Selective
recovery of the metal values
from the solution
 Sometimes includes
purification/concentration
Hydrometallurgy
 Purposes of hydrometallurgy:
 Recovery of salts – directly from their deposits. examples:
common salt, sodium carbonate, potash, borax, etc.
 Production of pure solutions - high purity metals can then be
produced by electrolysis, examples: zinc, cadmium, nickel,
copper, gold, and silver.
 Chemical beneficiation - undesirable components of the raw
material are leached away and the remaining solids are the
valuable product that has to be processed further. Examples:
desulfurization of coal
 Direct production of pure metals - suitable for the market after
a subsequent minor treatment. Examples: precipitation of
cobalt, nickel, and copper from solution by hydrogen under
pressure
Leaching
 Before leaching:
– usually crushed and ground
– sometimes beneficiated by physical methods.
 In some cases treated by thermal methods, such as
oxidation, reduction, before being leached:
– render the material more amenable to leaching, or
– exclude an undesirable component.
 Leaching is usually followed by:
 Filtration, washing, and
solution purification steps.
Leaching
 The choice of a leaching agent depends on the following factors:

– Solubility. Large and rapid solubility of the material to be

leached in the leaching agent.
– Cost. An expensive reagent is undesirable because any traces
lost during handling will represent a large economic loss.
– Materials of construction. If the leaching agent is corrosive
and has to be handled in tanks made of stainless steel,
titanium, or Hastalloy, the capital cost will be high, and
therefore its use will be less desirable.
– Selectivity. An ideal reagent will extract only the desired
component.
– Regeneration. Ability of regenerating the reagent for recycle
is also an important criteria.
Leaching-solubility
 Water molecules - high polarity
 But, Hydrogen bonds are weak
 Solubility of any substance in water
is related to the polarity of water and
the association of water molecules
together by forming hydrogen bonds.
 Ionic crystals: attractive forces
between the anions and cations in a
salt are reduced by a factor of 80
when water is the medium between
them
 Non-ionic crystals such as metals
(metallic bond) or covalent crystals
like quartz (SiO2) are insoluble
 Slightly soluble electrolytes are more
soluble in foreign salts than in pure
water
Leaching
 Water is an ideal leaching agent because it is cheap and
noncorrosive, but its action is only limited to few minerals.
 Leaching agents commonly used other than pure water are:
Acids, bases, and aqueous salt solutions
 Leaching agents may be used either alone or in
combination with oxidizing agents.
 An oxidizing or a reducing agent is sometimes needed
during leaching to solubilize certain minerals which do not
dissolve otherwise.
 Commonly used oxidizing agents are: oxygen (or air),
ozone, hydrogen peroxide, ferric ion, manganese dioxide,
sodium nitrate, and sodium chlorate
 Commonly used reducing agents are ferrous ion, hydrogen
and sulfur dioxide.
Leaching
 Sulfuric acid is the most common leaching agent.
 Dilute: used for leaching copper oxide ores, zinc oxide,
phosphate rock, and a variety of other ores.
 In combination with an oxidizing agent: used for leaching
uranium ores and sulfides.
 Concentrated: used for treating more resistant minerals such
as sulfide concentrates, laterites, monazite, and titanium slag.
Leaching

 Addition of oxygen to an
atom, ion, or molecule is
known as oxidation reaction.

Removal of oxygen is known

as reduction.
 Electrode (oxidation)
potential - The tendency of a
substance to be oxidized or
reduced, measured in volts
 For reactions involving
hydrogen ions, the electrode
potential is dependent on pH.
Leaching
 Leach general principles:

 Percent recovery is a major

concern
 Rate of a leaching process - the
percent recovery as a function of
time
 Related factors: particle size,
concentration of leaching agent,
temperature, pulp density,
agitation intensity
 Compromise is always made
between the increased rate of
leaching and the negative effect of
any of the factors influencing this
increase
Leaching
 Leach general principles:
 After leaching, slurries obtained are usually filtered/thickened to
recover the leach solution, then washed to remove entrained
solution from residues – CCD circuit
 Residues likely also need pH adjustment and heavy metal removal
Leaching
 Agitated pulp (tank) leaching:
 Leaching agent added to finely ground raw material, forms
a pulp
 Agitated continuously to prevent the solids from settling,
and to terminate the leaching process in the shortest
possible time.
 Generally used under the following conditions:
– The metal values are of fine grain size and disseminated
in the host rock - extensive crushing and grinding to
liberate.
– Raw material is of moderate to high grade.
– The metal values are difficult to dissolve and that is why
intensive agitation is needed to increase the rate.
Agitated Leaching
 Agitation may be accomplished in two ways:
 Mechanical: motor-driven impellers are used. More expensive capital and
maintenance cost.
 Pneumatic (Pachuca): 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
 High-pressure leaching:
 uses pressure reactors (or
autoclaves).
 Closed vessel
 temperature higher than the
boiling point
 Without oxidizing agent:
pressure generated is the result
of the vapor pressure of the
solution
 With oxidizing agent: oxygen
partial pressure is the
controlling factor on leaching
rate
Leaching
 High-pressure leaching:
 shape may be vertical or horizontal cylinders,
spherical, or a long horizontal tube
 Agitation: steam, mechanical impellers, or
rotating the whole autoclave
 Media is hot and corrosive: constructed of
special steel alloys, titanium, and other high-
grade materials. Interior may be lined with
rubber or ceramic.
 Usually connected in series for continuous
operation.
Leaching
 High-pressure leaching:

 Horizontal autoclave –
oxygen addition, cascading
flow. Fill to 65-70% to
allow space for the exhaust
gases

 Rotating autoclave –
contains grinding media to
expose mineral surface
(titanium ores)
In-situ Leaching
 The ore is simply leached in place over long periods of time because it is
usually too low in grade to justify mining and transportation expenses
 Two basic criteria required for an underground deposit to be
considered suitable for leaching in place are:
 The ore body must be enclosed between impermeable strata
that will prevent the loss of solution.
 It must be permeable to the leaching solution.
Heap/Dump Leaching
 Clear vegetation then level at a slight inclination
 cover with layer of asphalt or flexible plastic sheet
 Crushed ore transport from the mine to the prepared site by dump trucks
to a level of 10-15 m high
 The leaching agent is sprayed at the top of the dump through which it
percolates and the leach solution is collected at the bottom.
 When the material is fully leached, the dump is either abandoned or re-used
for leaching another batch.
Heap/Dump Leaching
 Material handling and stock-piling have become enormous
engineering operations.
 Problems include plugging with fine materials, evaporation losses,
leakage at the bottom, and channeling.
 Bio-heap leach using bacteria is commercial option
Terminology
 Purification/concentration operation:
 After leaching.
 Prior to precipitation.
 Goals: 1) purification and 2) increase solution concentration, from
which the metal values can subsequently be precipitated effectively.
 Methods used are:
– adsorption on activated charcoal,
– sorption on ion exchange resins
– extraction by organic solvents.
 Common operation scheme: loading, washing, and unloading (elution
or stripping) is used in all three operations.
 After the elution step, the material is ready for another cycle .
Purification and concentration
 Activated charcoal and
ion exchange processes
are often conducted in
columns
 Two main steps:
loading of the desired
metal and elution
(unloading)
 Water-washing
between these steps to
remove the entrained
solution.
 After the elution step,
the column is ready
again for loading
Purification and concentration
 Adsorption on activated charcoal:
 Used for concentrating gold and silver from cyanide leach solution
 Can be used for turbid solutions or pulps thus saving an expensive
filtration step.
 Low adsorption of metal ion by activated charcoal compared to ion
exchange; however, activated charcoal is a much cheaper material
 Charcoals heated at 400-800 °C produce a highly porous material called
"activated charcoal", usually in as pellets of 2 mm diameter
Purification and concentration
 Carbon adsorption and elution are slow processes: Typically it
takes about 24 hours to adsorb gold from a solution containing
about 10 ppm gold and 50 hours to elute.

 One ton activated carbon adsorbs about 10 kg gold.

 Three variations of the process are used: columns, carbon-in-pulp

and carbon-in-leach.

 Two factors contribute to the choice of the adsorption process:

» Filtration properties of the pulp
» Presence of organic matter in the ore
Purification and concentration
 Columns are used when the ore
can be filtered easily and clear
solutions can be obtained
 Carbon-in-pulp used to treat
ores containing clay particles
which are difficult to filter. Pulp
is agitated in tanks with the
charcoal pellets, then screened to
collect gold-laden pellets
 Carbon-in-leach used to treat
ores containing organic matter -
gold cyanide complex susceptible
of being lost in the residue.
Granular activated carbon is
added in the leaching tanks so
that it can adsorb the gold
cyanide complex ASAP.
Gold example
 Gold Cyanidation
 Pulp flows through a series of agitated tanks.
 Oxidative dissolution by hydrogen peroxide or air (or both).
 NaCN (0.32 gm l-1)
 pH is maintained at 10.0 by lime addition.
 4Au + 8NaCN + O2 + 2H2O  4Na+[Au(CN)2]- + 4NaOH
Ion exchange (IX)
 Natural (zeolite) or synthetic (polymer resin) material
 Uranium was the first metal to be recovered commercially using IX – paved the
way for other metals
 Especially useful in the treatment of very dilute solutions with metal ion
concentration of the order of 10 ppm or less
 An ion exchanger is a framework or a matrix (sponge) which carries a positive
or a negative electric charge.
 Counter-ions (holes) can be replaced by other ions of the same sign, while the
fixed ions (matrix) are not mobile.
Ion exchange (IX)
 Types of IX systems:
 Columns – fixed resin bed. Batchwise, carousel operation
Ion exchange (IX)
 Types of IX systems:
 Columns – fixed resin bed. Batchwise, carousel operation
Ion exchange (IX)
 Types of IX resins:

 Strong acid: cation exchangers,

containing -SO3H groups
 Weak acid: cation exchangers,
containing -COOH groups

 Strong base: anion exchangers.

Strength of the resin can be increased
by using substituted amines
 Weak base: anion exchangers,
containing amino groups
 Anion exchange.. The extracted
species is a negatively charged ion and
the extractant is a base, e.g., an amine:
Solvent extraction (SX)
 Leach solution is mixed with an immiscible organic solvent so the desired metal
ion in aqueous phase is transferred to organic phase
 The two phases are then allowed to separate.
 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.
 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 (SX)
 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
Separating funnel

Extraction Extract
Solvent

Feed Raffinate
Equipment
 Solvent extraction mixer-settlers
 Mixing chamber: aqueous and organic phases are mixed together by a rotating
impeller
 Settling chamber: mixed phases are given enough time to separate
Solvent extraction (SX)
 Only clear filtered solutions can be extracted
by organic solvents

 Usually many stages are used (3 to 5) and are

operated in counter-current in the extraction
as well as in the stripping steps.

 Sometimes, a washing step is inserted between

extraction and stripping to remove loosely
bound metal ions
Solvent extraction (SX)
equipment
 Krebs mixer-
settler:
 Mixer and
conical pump
 Top launder
for initial phase
disengagement
Solvent extraction (SX)
equipment

 Column cell:
 Discs and doughnuts
 No exposure to air
 Gentle mixing
Solvent extraction (SX)
equipment
 Outotec
Spirok mixers
 Low shear
Solvent extraction (SX)
 Organic typically has the following components:
 Carrier – main volume of organic, eg. kerosene
 Extractant – active in collecting metal. Eg. amine
 Diluent – Reduces surface tension, aids phase separation, eg.
Isodecanol (alcohol)
Hydrometallurgy
 Precipitation is the final step in many hydrometallurgical processes.
 It is also used as a purification step to separate impurities
 Can be physical or chemical
Hydrometallurgy
 Chemical precipitation methods:
 hydrolysis – just add water! Precipitation of oxides, hydrated
oxides, hydroxides, or hydrated salts
 Ionic - ions formed are neutralized by a base, example:
 Reduction - a reducing agent is added which results in the
precipitation of a metal and the agent is oxidized:

 An important sub-group is hydrogen reduction

 Substitution – precipitate metal ions from organic solvents
Precipitation
 Particle size

Particle size and form of a precipitate depend upon the

conditions of formation.

Freshly formed precipitate is sometimes described as

amorphous or gelatinous and is difficult to separate by filtration.

Precipitates undergo continuous recrystallization as they age ...

accelerated by heating
Precipitation
 Precipitation involves two steps:

– nucleation

– crystal growth

 Rate of nucleation is influenced by:

– concentration

– agitation

– nucleating agents

 Change in valency by adding an oxidizing or reducing agent may be used to effect selective
precipitations.
Extractive metallurgy
terminology
 Electrometallurgy – use of electrical energy
to induce a chemical transformation

– Electrowinning – to precipitate a metal

from solution using electric potential
– Electrorefining – to purify a metal by
dissolving it, then re-precipitating it
Electrometallurgy
 Electrolytic process:
 Precipitation of a metal from its aqueous solution is affected by imposing
an outside electromotive force from a direct current source. This can be
represented by:
Electrometallurgy
 Alternating anodes and cathodes in
a tankhouse for electrowinning
 For example, copper, zinc,
cadmium, and nickel are recovered
industrially from leach solutions by
electrolytic methods
 Example: Gold and silver are
recovered from the eluate by
electrolysis using steel wool
cathodes
 The aqueous solutions are
electrolyzed using inert electrodes;
the pure metal is deposited on the
cathode.
Extractive metallurgy
terminology
 Pyrometallurgy – use of heat to induce a chemical transformation
 Roasting – convert to oxide form. Often first step preceding
smelting for Cu, Ni, Pb
 Example: 2 CuS2 + 5 O2 → 2 CuO + 4 SO2
 Equipment – fluidized bed roaster
Extractive metallurgy
terminology
 Smelting - uses reducing substances that will combine with those
oxidized elements to free the metal.
 Example: 2 Fe2O3 + 3 C → 4 Fe + 3 CO2
 Converter – add back a bit of oxygen to purify, example: blister
copper
Pyrometallurgy equipment
 Smelter:
 Add flux (silica or lime) to remove impurities - waste becomes
slag
 Dust and off gas control are big issues
Pyrometallurgy

 The molten components coalesce, each forming an individual

molten layer
 Slag: top layer with specific gravity 3.6, and is composed of
silicates.
 Matte: next layer with specific gravity 5.2, and is composed
of sulfides.
 Speiss: next layer with specific gravity 6.0, and is composed
of arsenides.
 Bullion: bottom layer with specific gravity > 6, and is
composed of metals.
Pyrometallurgy
 Calcination – Chemical decomposition – but not oxidation or
reduction.
 Example: CaCO3 = CaO + CO2(g)
Pyrometallurgy-Gold smelting
 Gold-bearing sludge is mixed with NaNO3 flux.
 Heated to melting.
 Impurities transfer to the slag.
 Final gold product (Dore bar) is then poured, then
to refinery.
 Dore product composition:
90% Au
5-6% Ag
<5% Fe, Cu, Ni, ...
Thank you

Questions?