Suez University

Faculty of Petroleum and Mining Engineering

Metallurgical and Materials Engineering Department

Hydrometallurgy
Part 1

Prof. Dr. Eng. Ashour Owais

[email protected]

3rd Year
2020/2021
13-Oct-20 8:40 PM
 References

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1. Ghosh A. and Ray H. S., Principels of extractive
metallurgy, 2nd edition, New Age International
(P) Limited Publishers, New Delhi, 2001.
2. Terkel R., Principels of extractive metallurgy, 2nd
edition, McGraw-Hill book company, USA,
1983.
3. Gupta C. K., Chemical Metallurgy:Principles and
Practice, WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim, 2003.
4. http://en.wikipedia.org/wiki/Hydrometallurgy
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 Introduction

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Extractive metallurgy is the study of the processes
used in the separation and concentration
(beneficiation) of raw materials.

The field of extractive metallurgy encompasses

many specialty sub-disciplines, each concerned with
various physical and chemical processes that are
steps in an overall process of producing a particular
material.

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These specialties are generically grouped into the
categories of mineral processing, hydrometallurgy,
pyrometallurgy, and electrometallurgy.
The theoretical basis of extractive metallurgy is
underpinned by the more general sciences of
physics, chemistry, and geology.

Additionally, the practice of extractive metallurgy

nearly always involves contributions from other
scientific fields such as analytical chemistry and
mineralogy.
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Mineral processing

Mineral processing involves the processes used to

manipulate the particle size of solid raw materials
and to separate valuable materials from materials of
no value, referred to as gangue.

Usually, particle size reduction, also referred to as

comminution, is required to permit efficient
separation of the valuable materials from gangue.

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Separation processes take advantage of physical
properties of the materials in order to separate them
from each other.

These physical properties can include density,

particle size and shape, electrical and magnetic
properties, and surface properties.

Since many size reduction and separation processes

involve the use of water, solid-liquid separation
processes are also a subject of mineral processing.
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Pyrometallurgy

Pyrometallurgy involves high temperature processes

where chemical reactions take place among gases,
solids, and molten materials.

Solids containing valuable metals are reacted to

form intermediate compounds for further processing
or converted into their elemental or metallic state.

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Pyrometallurgical processes that involve gases and
solids are typified by calcining and roasting
operations.

Processes that produce molten products are

collectively referred to as smelting operations.

The energy required to sustain the high temperature

pyrometallurgical processes may come entirely from
the exothermic nature of the chemical reactions
taking place, usually oxidation reactions.
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Often, however, energy must be added to the process
by combustion of fuel or, in the case of some
smelting processes, by the direct application of
electrical energy.

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Hydrometallurgy

Hydrometallurgy is concerned with processes

involving aqueous solutions to extract metals from
ores.

The most common hydrometallurgical process is

leaching, which involves dissolution of the valuable
metals into the aqueous solution.

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After the solution is separated from the ore solids,
the solution is often subjected to various processes
of purification and concentration before the valuable
metal is recovered either in its metallic state or as a
chemical compound.

The solution purification and concentration

processes may include precipitation, distillation,
adsorption, and solvent extraction.

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The final recovery step may involve precipitation,
cementation, or an electrometallurgical process.

Sometimes, hydrometallurgical processes may be

carried out directly on the ore material without any
pretreatment steps.

More often, the ore must be pretreated by various

mineral processing steps, and sometimes by
pyrometallurgical processes.
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Electrometallurgy

Electrometallurgy involves metallurgical processes

that take place in some form of electrolytic cell.

The most common types of electrometallurgical

processes are electrowinning and electrorefining.

Electrowinning is an electrolysis process used to

recover metals in aqueous solution, usually as the
result of an ore having undergone one or more
hydrometallurgical processes.
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The metal of interest is plated onto the cathode,
while the anode is an inert electrical conductor.

Electrorefining is used to dissolve an impure

metallic anode (typically from a smelting process)
and produce a high purity cathode.

Fused salt electrolysis is another electrometallurgical

process whereby the valuable metal has been
dissolved into a molten salt which acts as the
electrolyte, and the valuable metal collects on the
cathode of the cell.
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The fused salt electrolysis process is conducted at
temperatures sufficient to keep both the electrolyte
and the metal being produced in the molten state.

The scope of electrometallurgy has significant

overlap with the areas of hydrometallurgy and (in
the case of fused salt electrolysis) pyrometallurgy.

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 Mineral Processing

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Mineral processing is a major division in the science
of Extractive Metallurgy.
The field of mineral processing has also been given
other titles such as mineral dressing, ore dressing,
mineral extraction, mineral beneficiation, and
mineral engineering.
In mineral processing, a number of unit operations
are required to prepare and classify ores before the
valuable constituents can be separated or
concentrated and then forwarded on for use or
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further treatment.
Ores and Minerals

Ore is a term used to describe an aggregate of

minerals from which a valuable constituent,
especially a metal, can be profitably mined and
extracted.

Most rock deposits contain metals or minerals, but

when the concentration of valuable minerals or
metals is too low to justify mining, it is considered
as a waste or gangue material.
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Within an ore body, valuable minerals are
surrounded by gangue and it is the primary function
of mineral processing, to liberate and concentrate
those valuable minerals.

A list of some valuable minerals is provided in the

following Table.

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 Metal Ore Mineral Chemical Formula
Aluminum Bauxite Al2O3·3H20
Chromium Chromite FeCr2O4
Cobalt Skutterudite (Co,Ni,Fe)As3
Chalcopyrite CuFeS2
Copper Chalcocite Cu2S
Bornite Cu5FeS4
Iron Hematite Fe2O3
Magnetite Fe3O4
Lead Galena PbS
Cerusite PbCO3
Magnesium Dolomite (Ca,Mg)CO3
Magnesite MgCO3
Manganese Pyrolusite MnO2
Mercury Cinnabar HgS
Nickel Pentlandite (Fe,Ni)9S8
Tin Cassiterite SnO2
Titanium Ilmenite FeTiO3
Rutile TiO2
Uranium Uraninite UO2
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Zinc Sphalerite ZnS
In broader terms, mineral processing consists of two
functions.

Firstly, it involves the preparation and liberation, of

the valuable minerals from waste minerals and
secondly, the separation these values into two or
more products, called concentrates.

The term separation in this case is synonymous with

concentration.

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The following flowsheet shows diagrammatically
the typical sequence of operations in the process
plant.

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Liberation and Comminution

Liberation

In order to separate the minerals from gangue (the

waste minerals), it is necessary to crush and grind
the rock to unlock, or liberate, valuable minerals so
that they are partially or fully exposed.

This process of size reduction is called

comminution.
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The crushing and grinding process will produce a
range of particles with varying degrees of
liberation.

Any particles that exceed a target size required for

physical separation or chemical extraction are
returned to the crushing or the grinding circuit.

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Breaking of larger material to smaller pieces result in particles with
varying degrees of liberation.
(The darker regions represent the valuable mineral)

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Comminution
The comminution process actually begins during the
mining stage through the use explosives, excavators
or scrapers for softer material.

This is necessary in order to generate a material that

is transportable by haul trucks or conveyors.

Comminution in the mineral processing plant is

carried out in a sequential manner using crushers
and screens followed by grinding mills and
classifiers.
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Crushers:

• Jaw crusher
• Gyratory crusher
• Cone crusher
• Rolls crusher
• Horizontal shaft impactor (HSI) crusher
• Vertical shaft impactor (VSI) crusher

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Grinding machines:

• Ball mill
• Rod mill
• SAG mill (Semi-Autogenous Grinding)
• AG (Autogenous) mill
• Pebble mill
• High pressure grinding rolls
• Buhrstone mill
• Vertical shaft impactor (VSI) mill
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Screening:
In its simplest configuration, a screen is a hard
perforated surface with a matrix of fixed dimension
apertures.

The material is presented to the screen surface so

that material finer than the apertures falls through
the screen and the oversize is conveyed to the
discharge end of the screen.
Screening is generally difficult below 0.5 mm.
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Classification:
Classification techniques takes advantage of the
principle that particles of the same density but of
different sizes settle in a fluid at different rates.
Exploiting the difference in the settling rates allows
for separation based on size.

Classification is usually carried out at particle sizes

that are considered to be too fine for sorting
efficiently by screening methods.
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Separation and Concentration Techniques
The separation and concentration of the valuable
mineral can take place after the ore is crushed,
ground, and classified into the required particle size
distribution.

There is a number of different techniques whuch

employed in concentrating the valuable minerals.
These techniques exploit differences in physical or
chemical properties of the valuable and gangue
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minerals.
Separation Methods

i. Sorting – based on appearance, colour, texture,

optical properties and radioactivity

ii. Gravity and Dense-Medium Separation

Separation based on specific gravity of the valuable

mineral relative to the gangue and the carrying
medium such as water.
In dense-medium separation, the carrying medium
is a mixture of water, magnetite, or ferrosilicon.
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iii. Magnetic Separation – separation based upon
natural or induced differences in magnetic
susceptibility of the minerals within the ore.

iv. Froth Flotation - separations based on the

surface chemistry properties of a mineral.

The natural or modified surface property of the

mineral determines its ability to attach to an air
bubble and float to the surface.

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 Pyrometallurgy

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Pyrometallurgy is a branch of extractive metallurgy.

It consists of the thermal treatment of minerals and

metallurgical ores and concentrates to bring about
physical and chemical transformations in the
materials to enable recovery of valuable metals.
Pyrometallurgical treatment may produce saleable
products such as pure metals, or intermediate
compounds or alloys, suitable as feed for further
processing.
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Examples of elements extracted by
pyrometallurgical processes include the oxides of
less reactive elements like Fe, Cu, Zn, Chromium,
Tin, Manganese.
Pyrometallurgical processes are generally grouped
into one or more of the following categories:
* Drying * Calcining
* Roasting * Smelting
* Refining
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Most pyrometallurgical processes require energy
input to sustain the temperature at which the process
takes place.
The energy is usually provided in the form of fossil
fuel combustion, exothermic reaction of the
material, or from electrical heat.
When enough material is present in the feed to
sustain the process temperature solely by exothermic
reaction (i.e. without the addition of fuel or electrical
heat), the process is said to be "autogenous“.
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Drying
Drying is thermal removal of liquid moisture (not
chemically bound) from a material.

Drying is usually accomplished by contacting the

moist solids with hot combustion gases generated by
burning fossil fuels.
In some cases, heat for drying can be provided by
hot air or inert gas that has been indirectly heated.

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The amount of heat required for a given drying
operation corresponds to the heat required to
vaporize the liquid moisture, the heat required to
raise the temperature of the products (dry solids and
water vapor) to the final drying temperature, and
heat required to offset radiant heat losses.

Usually the drying temperature is set at a nominal

value above the boiling point of water, often about
120°C.

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In special cases, such as in the drying of certain
water-soluble salts, higher drying temperatures are
required.

In salt drying, the feed moisture is saturated with

dissolved salts, which alters the boiling point and
requires higher drying temperatures.

Drying of moist solids is carried out in several types

of industrial dryers, including rotary dryers,
fluidized bed dryers, and flash dryers.
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Another type of drying, called spray drying, is
carried out when the material to be dried is
completely dissolved in aqueous solution.

The solution is sprayed (usually through a specially

designed nozzle) into a heated chamber and as the
water is evaporated, solids crystallize.

The water vapor is exhausted from the dryer, and

dry solids are collected, usually in a conical section
of the dryer.
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 Spray drying

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 Spray drying

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Solid material produced from a spray dryer often has
special particle size and shape characteristics, which
may be controlled by the concentration of dissolved
material in the solution, and the design of the
atomizing spray nozzle.

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Calcining

Calcining is thermal decomposition of a material.

Examples include decomposition of hydrates such as
ferric hydroxide to ferric oxide and water vapor, or
decomposition of calcium carbonate to calcium
oxide and carbon dioxide and or of iron carbonate to
iron oxide.
Calcination processes are carried out in a variety of
furnaces, including shaft furnaces, rotary kilns, and
fluidized bed reactors.
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Examples of chemical decomposition reactions
common in calcination processes, and their
respective thermal decomposition temperatures
include:

CaCO3 → CaO + CO2; at ~ 900 °C

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Roasting

Roasting consists of thermal gas-solid reactions,

which can include oxidation, reduction, chlorination,
sulfation, and pyrohydrolysis.
The most common example of roasting is the
oxidation of metal sulfide ores.
The metal sulfide is heated in the presence of air to a
temperature that allows the oxygen in the air to react
with the sulfide to form sulfur dioxide gas and solid
metal oxide.
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For the ores Cu2S (chalcocite) and ZnS (sphalerite),
balanced equations for the roasting are:

2 Cu2S + 3O2 → Cu2O + 2 SO2

2 ZnS + 3 O2 → 2 ZnO + 2 SO2

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The solid product from roasting is often called
"calcine“.
In sulfide roasting, if the temperature and gas
conditions are such that the sulfide feed is
completely oxidized, the process is known as "dead
roasting."

Sometimes, as in the case of pre-treating

reverberatory or electric smelting furnace feed, the
roasting process is performed with less than the
required amount of oxygen to fully oxidize the feed.
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In this case, the process is called "partial
roasting," because the sulfur is only partially
removed.
Finally, if the temperature and gas conditions are
controlled such that the sulfides in the feed react to
form metal sulfates instead of metal oxides, the
process is known as "sulfation roasting“.

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Sometimes, temperature and gas conditions can be
maintained such that a mixed sulfide feed (for
instance a feed containing both copper sulfide and
iron sulfide) reacts such that one metal forms a
sulfate and the other forms an oxide, the process is
known as "selective roasting" or "selective
sulfation."

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Smelting
Smelting involves thermal reactions in which at least
one product is a molten phase.
Metal oxides can then be smelted by heating with
coke or charcoal (forms of carbon), a reducing agent
that liberates the oxygen as carbon dioxide leaving a
refined metal.
Concern about the production of carbon dioxide is
only a recent worry, following the identification of
the enhanced greenhouse effect.
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Carbonate ores are also smelted with charcoal, but
are sometimes need to be calcined first.
Other materials may need to be added as flux, aiding
the melting of the oxide ores and assisting in the
formation of a slag, as the flux reacts with
impurities, such as silicon compounds.
Smelting usually takes place at a temperature above
the melting point of the metal, but processes vary
considerably according to the ore involved and other
matters.
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Refining
Refining is the removal of impurities from materials
by a thermal process.

This covers a wide range of processes, involving

different kinds of furnace or other plant.
The term, 'refining' can also refer to certain
electolytic processes.
Accordingly, some kinds of pyrometallurgical
refining are referred to as 'fire refining'.
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 Hydrometallurgy

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Hydrometallurgy is a part of the field of extractive
metallurgy involving the use of aqueous chemistry
for the recovery of metals from ores, concentrates,
and recycled or residual materials.

Hydrometallurgy refers to production of metals or

pure compounds with the help of reactions in
aqueous and organic solutions.

It is a process of beneficiation as well as extraction.

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Hydrometallurgical treatments are usually carried
out on low grade ores which are normally not
suitable for pyrometallurgical operations, and as rich
ore bodies gradually get exhausted, metallurgists
have to depend more and more on hydrometallurgy.

Hydrometallurgical processing involves the

following steps:

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1- Leaching: During leaching the desired elements
in the ore are selectively dissolved in an appropriate
solvent known as the leaching reagent or leachant.
Proper leaching may call for some preliminary ore
preparation operations such as grinding, sizing,
physical beneficiation, roasting etc.
2- Separation and concentration of leach liquor:
In this step, the solution i.e. the leach liquor is
separated from solid residues by one or more of the
various methods of materials separation, viz.
settling, thickening, filtration, washing, ion
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exchange, solvent extraction etc.
3- Recovery of metallic values from leach liquor:
The desired solute or the metal in elemental form is
obtained in the recovery step. Methods employed to
treat the enriched liquor include evaporation,
distillation, precipitation, cementation, electrolysis,
etc.

4- Reagent recovery: The leaching agent is

generally recycled after purification and
readjustment of composition.
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 Ore / concentrate
Oxidant Leaching agent

leaching

Solid-liquid separation Solid residu to

waste
Pregnant Solution

Precipitant or
Solution purification electric current

Precipitation

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Pure compound Metals
71
Any hydrometallurgical process consisting of these
steps may have one of the following objectives.
• To produce a pure compound which can be later
processed to a metal by pyrometallurgical
methods. Here hydrometallurgy is only a
beneficiation step.
• To produce a metal from either crude metal or
metal compound which has been prepared earlier
by other methods.
• To produce a metal directly from an ore or
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concentrate.
Hydrometallurgy development
Hydrometallurgy is developed after pyrometallurgy.
Metals smelting has been practiced since thousands
years ago.
Hydrometallurgy was developed after the people
discovered acid and base solutions.

However, modern hydrometallurgy development is

commonly associated with the invention of Bayer
Process for bauxite leaching and cyanidation for
gold extraction at the end of 19th century (1887).
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One of important highlights of hydrometallurgy
development is uranium extraction (Manhattan
Project) aimed at nuclear weapon production in
second world war (1940‘s).

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Advantages and Disadvantages of
Hydrometallurgy
Hydrometallurgical processing is characterized by
several distinct advantages. These are listed.

1. Hydrometallurgical methods are suited for lean

and complex ores.
With gradual depletion of rich ore deposits, it is
becoming increasingly difficult in many situations to
apply conventional pyrometallurgical methods for
metal extraction.
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If there is too much gangue, then processing ores at
high temperatures causes wastage of energy as well
as problems of slag disposal.

The siliceous gangue in ore is unaffected by most

leaching agents; whereas in pyrometallurgical
smelting processes, the gangue must be slagged.

2. Hydrometallurgy allows greater control over

every step in processing of ores resulting in
recovery of valuable by-products.
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3. Metals may be obtained directly in a pure form
from the leach liquor using one of several
methods. Handling of materials is also easier.

4. Hydrometallurgical operations are often

preferable from the point of view of reducing
environmental pollution.
Thus while pyrometallurgical processing of
sulphides ores, e.g. copper ores produce SO2,
leaching of ores keep sulphur in solution.
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SO2 liberated during roasting of sulphides as well as
during the other steps in pyrometallurgical
processing, is not always suited for use in H2SO4
production.

Even if it is used in acid production, there is still

escape of SO2, in air unless stringent antipollution
measures are effected.
5. A hydrometallurgical process may start on a small
scale and expand as required.
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However, a pyrometallurgical process usually must
be designed as a large scale operation for reasons of
process economy.

There are some other advantages as well.

For example, in some hydrometallurgical recovery,

the metal can be produced in a variety of physical
forms e.g., powder, nodule, coherent surface deposit
etc.

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Again, very reactive metals are difficult to refine by
pymmetallurgical methods.

Therefore, pure compounds can be first obtained by

hydrometallurgy and then reduced to pure metal.

Also, corrosion problems are relatively mild in

hydrometallurgy as compared with deterioration of
refractory linings which requires periodic shutdown
in pyrometallurgy.

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The disadvantages of hydrometallurgy are as
follows:
1. Aqueous solutions employed are generally dilute
(of the order of one molar.)

Thus large volumes of solutions are to be handled

for relatively smaller metal outputs. This requires
considerable amount of handling as well as space.

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2. Some reagents are expensive and must be
recycled or regenerated for economy.
3. Reaction rates are lower at room temperatures as
compared to processing at high temperatures.
Hence tonnage capacity of a plant is lower as
compared to that obtainable in pyrometallurgy.

On the whole, however, the advantage often

outweigh the disadvantages and hydrometallurgy is
becoming increasingly important for many
nonferrous metals.
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Hydrometallurgy vs. Pyrometallurgy
In conclusion, Hydrometallurgy will displace
inefficient Pyrometallurgy processes in time.
There are at least two examples which bear witness
to this:
1) Zinc was produced for over 400 years by a fully
pyrometallurgical route. Since 1980, a fully
hydrometallurgical process was invented (Sherritt
autoclave process) and four plants are now in
operation using this technology.
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2) Alumina was first produced by a high temperature
sintering process (Le Chatelier, 1855) was
replaced by Bayer's hydrometallurgical process in
1892 - the process used today world wide.

Hydrometallurgy has also broadened the metal

extraction options, as a more obvious extraction
option as compared to pyrometallurgy.

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