Hydrometallurgical Principles
leaching. High-grade materials such as concentrates
In hydrometallurgical extraction of metals, the major
process steps take place in liquid phases, pre-
dominantly aqueous solutions. Two basic unit pro-
cesses are involved: (a) the leaching or dissolution of
the value(s) contained in solids; and (b) the subsequent
separation, purification, and recovery of these values
(Gupta and Mukherjee 1990, Hayes 1993, Gill 1980).
As shown in Fig. 1, actual hydrometallurgical pro-
cesses often incorporate additional unit operations.
These steps may include preleach treatment of the
feed, separation of liquids and solids, conditioning of
the pregnant leach solution, disposal of leach residues,
and treatment of barren solution before discharge or
recycle.
Hydrometallurgical systems have been designed to
handle a wide range of feed materials and to produce
many different metals. The product may be of high
purity, like zinc produced in a leach-electrowinning
circuit. It may also be impure, requiring upgrading, as
in metals precipitated by cementation. Finally, the
product may be a high-grade intermediate such as
Bayer process aluminum hydroxide, Al(OH) , or
yellow cake, U O , derived from uranium leaching. $
$ )
1. Raw Material
The material being leached varies widely in grade.
However, process chemistry is sensitive to the charac-
teristics of the raw material. Thus, each process must
be designed for a specific input. The material can be
lean overburden stripped simply to expose higher-
In-situ
leaching
Figure 1
General flow diagram for a hydrometallurgical process.
grade ore, or richer materials mined expressly for
are also used for hydrometallurgical processing.
The wide range of feeds that can be treated by
hydrometallurgy contrasts sharply with pyrometal-
lurgy (see Pyrometallurgy). Pyrometallurgical pro-
cessing is generally limited to a high-grade feed
because of the cost of melting and slagging off the
gangue.
2. Preleach Treatment of Raw Material
Preleach treatment usually starts with size reduction.
This accelerates leaching or makes the minerals amen-
able to concentration. Flotation is a preferred method
of concentration, particularly for sulfide minerals.
This method takes advantage of the difference in the
affinity of solid surfaces toward air and water. In this
process, gas (usually air) bubbles are injected into the
bottom of a slurry that contains fine, solid particles.
Certain minerals (such as sulfides) are hydrophobic,
and thus attach themselves to the gas bubbles and rise
to the top, leaving hydrophilic particles (such as silica)
behind. Other concentration methods are based on
differences in specific gravity, magnetic property, or
electrostatic property. There is always a loss of mineral
values during concentration, and its minimization is
an important aspect of any concentration process.
In some cases, chemical pretreatment is necessary to
facilitate the leaching of metals to be recovered and\or
to render the gangue components less soluble. Sulfide
minerals are often roasted to sulfates, which are much
more readily soluble in water, and the accompanying
iron is oxidized into insoluble iron oxides. In other
cases, the mineral is reduced to the elemental metal
before being leached, as in the recovery of nickel (and
cobalt) from lateritic ores. Refractory and\or car-
bonaceous gold ores are roasted to transform the
pyrite to iron oxide, which is more porous, and to burn
off the organic carbon that robs the gold from the
leach solution (Fernandez et al. 2000). Both of these
factors contribute to the increase in gold recovery in
the subsequent leaching by a cyanide solution.
3. Leaching
Following pretreatment, the material is subjected to
leaching. Water alone can solubilize most sulfates
formed during roasting of the sulfides. Acids, however,
are the most common lixiviants (leaching agents).
Sulfuric acid can be used on oxide or silicate ores to
extract copper, zinc, and uranium. Where effective,
sulfuric acid is preferred because of its low cost and
availability as a by-product of sulfide smelting. Other
favorable properties of sulfuric acid include very low
volatility and high chemical stability in aqueous
solutions. The use of other acids such as nitric or
1
Hydrometallurgical Principles
hydrochloric acids is limited to specific systems owing
to undesirable properties such as high cost, volatility,
chemical instability, and corrosiveness.
Alkaline lixiviants are also used, the most common
being sodium hydroxide. It is used in the Bayer process
to refine bauxite to purified alumina. Ammonia is also
used on account of its selectivity for certain metals
such as nickel and copper and because it is not
corrosive. Certain salts can also act as lixiviants; e.g.,
alkaline cyanide has long been employed in leaching
gold and silver.
All lixiviants should satisfy two important require-
ments: selectivity and rapid leaching rate. Selectivity
should not only apply between different metal values
but also to gangue components. Dissolution of the
gangue causes the problems of lixiviant consumption,
impurity addition, and decrepitation of the host rock
matrix. The last occurrence causes several difficulties,
including the reduced flow or access of solution
necessary for leaching and the generation of slimes
that causes difficulty in the subsequent liquidsolid
separations and in the residue-washing step to com-
pletely recover the dissolved solutes.
Leaching reactions may be classified into the fol-
lowing broad categories:
(i) Physical dissolution. In this process, a solid
dissolves without undergoing chemical changes, as in
the following example:
CuCl (s) Cu#+(aq)j2ClV(aq) (1)
#
(ii) Chemical dissolution. In this case, the solid has a
low solubility, often due to the presence of a covalent
bond in the crystal structure, but becomes soluble by
reacting with agents dissolved in the solvent (water):
ZnO(s)jH SO (aq) ZnSO (aq)jH O (2)
# % % #
(iii) Electrochemical dissolution. This process is
characterized by the occurrence of electron transfer in
the solid phase, i.e., a reductionoxidation (redox)
reaction couple is involved. The simplest example is
the dissolution of an elemental metal in an acid:
Znj2H+ Zn#+(aq)jH (3)
# Fe#+ ,,- Fe$+jeV
in which the metal is oxidized. In other examples, a
metal cation is reduced to the soluble state:
MnO (s)j4HCl(aq) MnCl (aq)j2H OjCl
# # # #(4)
Redox reactions often require the addition of an
oxidizing or reducing agent, as in the following
example of gold leaching:
4Au(s)j8CNVjO j2H O 4[Au(CN) ]Vj4OHV
# # # (5)
in which oxygen gas is the added oxidant.
2
Compared with pyrometallurgical reactions which
take place at high temperatures and thus at high rates,
hydrometallurgical processes, especially leaching, are
much slower. The slow leaching reactions are often
compounded by the buildup of a product or depleted
gangue layer around the unleached portion. Fur-
thermore, parts of the metal or mineral to be leached
may be present in a refractory form that resists
dissolution (Fernandez et al. 2000) or tightly sur-
rounded by an impervious layer of inert mineral
phases. These occurrences may make the leaching rate
prohibitively slow so as to lower the overall degree of
recovery.
The configuration of a leaching process depends on
the ore grade and characteristics as well as the value of
the metal to be recovered. Four typical leaching
systems are illustrated in Fig. 2. High-grade concen-
trates are leached in a vessel agitated mechanically or
by air injection. Agitation leaching offers rapid and
complete dissolution of values by making it possible to
use fine feed particles, elevated temperature, and
pressurization for increased solubility of gaseous
reactants. Moderate-grade ores are typically crushed
and leached in heaps, which takes from a few weeks to
months. Low-grade overburden or mine waste that
still contains mineral values may be leached in a dump
consisting of as-mined rocks designed mainly to
minimize mining costs rather than optimize extraction
(Sohn and Wadsworth 1979). It may take up to several
years to recover a significant portion of values.
The rates of reactions in the heap and dump leaching
processes are often enhanced by the participation of
bacteria (Gupta and Mukherjee 1990, Paul et al.1992).
For example, in copper dump leaching the leaching
reaction is:
CuFeS jFe (SO ) CuSO j3FeSO j2S!
# # %$ % % (6)
In order for the leaching process to continue, the
ferrous sulfate needs to be reoxidized. The bacteria
Thiobacillus ferrooxidans assist in this reoxidation
process, as follows:
bacteria
(7)
together with
bacteria
S!jH Oj1.5O ,,- H SO (8)
# # # %
The in situ leaching or solution mining process avoids
a significant part of the costs involved in mining,
materials handling, and concentration. To be amen-
able to in situ leaching, the ore deposit should undergo
in situ fracturing or be naturally permeable. A fairly
successful example of this leaching method is the
extraction of uranium from a permeable sandstone

Figure 2
Typical leaching systems: (a) agitation leaching, (b) heap leaching, (c) dump leaching, (d) in situ leaching.
deposit. In situ leaching processes, however, suffer
from low recovery and difficulties in controlling the
liquid flow. Furthermore, the risk of environmental
contamination due to the leakage of leach solution
presents a serious challenge.
4. LiquidSolid Separation
Pregnant leach solution must be completely recovered
from the solids so that the residue can safely be
disposed of as well as to increase the yield of values.
Leach solutions or slurries often contain fine par-
ticulates generated from feed decrepitation or chemi-
cal precipitation. These are difficult to settle, filter, and
wash, and often cause a liquidsolid separation to
become a very expensive operation. Such an operation
Hydrometallurgical Principles
generally requires multistage countercurrent washing
in large thickeners. For small tonnages of solids,
filtration and wash systems may be used.
5. Solution Purification and Concentration
The pregnant solution from the liquidsolid separ-
ation step must undergo further purification. The
simplest treatment may just involve a final filtration
step or adjustment of solution pH or oxidation
potential. More often than not, however, the purifi-
cation step involves complex procedures of impurity
removal, separation of dissolved values, and con-
centration of the solution. Certain impurities can be
removed by selective chemical precipitation or cemen-
tation based on the same principles that are applied to
3
Hydrometallurgical Principles
the recovery of values discussed below. However, in
many cases the pregnant solutions contain low con-
centrations of the metal to be recovered, have two or
more metals of value dissolved (that may have similar
chemical properties), and\or are highly contaminated
with several impurities. Three commonly used
methods for treating these types of solutions will be
discussed. It will be noticed that all these processes
closely combine the purification and separation steps
with concentration of the solution.
The most extensively used method is solvent ex-
traction (SX), which involves contacting the pregnant
leach solution with an organic liquid containing an
active extractant and appropriate modifiers dissolved
in a solvent (diluent). The leach solution and the
organic liquid form immiscible phases and must have
low mutual solubilities. Upon contacting, the dis-
solved metal or metal complex ions and the extractant
molecules undergo chemical exchange reactions. The
reaction may involve cation exchange, anion ex-
change, or neutral incorporation of solutes into the
extractant molecules. The extractant should have high
selectivity toward the metal to be extracted, and permit
reversible stripping of the extracted metal value and
regeneration of the organic liquid when contacted
with a fresh aqueous solution under suitable con-
ditions. The contacting of the two phases is carried out
in a liquidliquid emulsion of the aqueous and the
organic phases. The emulsion provides a large inter-
facial area for rapid transfer of solutes from one phase
to the other, but should not contain too many very
small droplets that do not coalesce readily during
phase disengagement. The emulsion is generated either
by mechanical stirring, as in mixer-settlers, or by
spraying one liquid into the other, as in spray columns.
Other liquidliquid mixing devices, such as centrifugal
contactors and static mixers, are also used. In the
centrifugal contactor the two immiscible liquids are
squeezed through small-diameter holes to enhance
mass transfer, and centrifugal force is used to magnify
the effect of density difference between the two liquids
for rapid phase disengagement. The static mixer
consists of a housing that contains a stationary internal
structure which breaks up the liquids to generate the
emulsion when they are forced to flow through the
device. In one solvent extraction process, the liquid
liquid emulsion is generated by injecting high-strength
gas jets at certain intervals from the bottom of a
horizontal cylindrical vessel through which the two
liquids flow countercurrently (Sohn 1997). This con-
tacting method avoids complex mechanical stirring
devices as well as interstage pumping and piping,
while providing adequate interfacial area (Sohn and
Doungdeethaveeratana 1998).
Extraction or loading is generally carried out by
moving the pregnant solution and the organic liquid
countercurrently through several stages if contacting
is in stages as in mixer-settlers, or over a sufficient
length if contacting is differential as in columns. The
4
loaded organic liquid is physically separated and
brought into contact with an aqueous solution to strip
the metal from the organic phase back into the
aqueous solution by providing conditions that will
reverse the extraction reaction. Stripping generally
yields purified solutions at much higher concentrations
of the metal value. In some cases, the loaded organic
phase is first scrubbed before stripping, by being
brought into contact with an aqueous scrubbing
solution to selectively remove from the loaded organic
solvent unwanted metals that were extracted together
with the metal to be recovered. Further details of the
various solvent extraction contactors and process
principles can be found in the literature (e.g., Ritcey
and Ashbrook 1978, Lo et al. 1983).
Ion exchange (IX) refers to a reversible chemical
reaction involving ion transfer between a solid and an
aqueous solution. The ions that are transferred may be
cations or anions, and the solid is generally an organic
resin. Pregnant leach solution is passed through a bed
of resin to load the metal. Then the resin is tripped to
produce a small volume of concentrated and purified
solution. A major advantage of ion exchange is
recovery of metals from very dilute solutions. A
common problem is poisoning of the resin by im-
purities that are not easily removed. When the capacity
of the resin is substantially reduced by the presence of
these impurities, it requires regeneration by using
strong solutions of suitable reagents that will strip the
impurities from it.
Certain pregnant leach solutions, mainly solutions
of gold and silver from the cyanide leaching process,
are purified by selectively adsorbing the dissolved
metal onto an active charcoal surface. The loaded
charcoal is subsequently eluted to recover the metal in
a purified and concentrated solution (Gupta and
Mukherjee 1990).
6. Metal Recovery
The values in the purified and concentrated solutions
are recovered by electrowinning, reduction with a gas,
cementation, precipitation as compounds, or crystalli-
zation of compounds.
Electrowinning involves electrolytic reduction of
metal ions by imposing an electric potential in the
solution. At the cathode, the following reaction takes
place:
Mn+jneV M! (9)
and at the anode the predominant reaction is:
n\2H O n\4O (g)jnH+jneV (10)
# #
The overall reaction then is:
Mn+jn\2H O M!jn\4O (g)jnH+ (11)
# #
 Hydrometallurgical Principles

Table 1
Comparison of hydrometallurgy and pyrometallurgy.
Hydrometallurgy Pyrometallurgy
Adantages
Low capital costs for small-scale operations Use of cheap oxygen as a major reactant
Suitable for low-grade or complex ores Use of sulfur in the mineral or cheap carbon as a fuel
Suitable for nonferrous base metal oxides Generation of stable solid waste
Ease of transfer of process streamssolutions or slurries Nearly 100% value recovery including precious
metals as by-products
Simple process steps
High throughput rates
Insensitive to feed uniformity
Disadantages
Large consumption of electric power and other fuels Handling of molten materials
Requirement of various and expensive reagents Severe process conditions
Complex plant engineering Large metal inventory
Generation of liquid and solid wastes that
pose serious disposal problems
Slow reaction rates
Low throughput rates
Requirement for uniform feed
Difficulty of recovering precious metals as by-products

Operating parameters such as acid and metal concen- crystals of the metal to the autoclave will also
trations and electrolyte temperature must be con- accelerate precipitation by providing nucleation sites
trolled to obtain good cathode quality. Costs are and avoiding supersaturation.
minimized by maintaining a high current efficiency Other gases such as carbon monoxide and sulfur
(i.e., using virtually all of the applied current to deposit dioxide are sometimes used as the reductant. An
the metal). One of the chief detriments to this is the example of the reaction involving sulfur dioxide gas is:
presence of impurities in the electrolyte which exhibit
a multiple valency. These will consume current by SO jH O H+jHSOV (13)
establishing a redox couple, being oxidized at the # # $
Cu#+jHSO jH O CujHSO j2H+ (14)
V V
anode and reduced at the cathode. $ # %
A disadvantage of electrowinning is that it is more
energy intensive than electrorefining of the same metal. Reactive metals such as uranium, vanadium, mol-
In the latter, the half-cell reactions are dissolution of ybdenum, and tungsten cannot be reduced to elements
the impure metal from the anode and cathodic by hydrogen reduction in the aqueous phase. Rather,
deposition of that same metal in a refined form. Since hydrogen reduction leads to the precipitation of their
the voltage required for dissolution is less than the lower oxides, as exemplified by the following reactions:
overvoltage needed for water decomposition, the
MoO#VjH MoO j2OHV (15)
power required is less than that required by electro- % # #
winning. Thus, when combined with the autogenous UO (CO )% jH
V
UO j2HCO jCO# (16)
V V

or semiautogenous nature of most smelting processes, # $$ # # $ $

hydrometallurgy often has a higher energy require-
ment than pyrometallurgical treatment of the same
feed.
Reduction with a gas to recover metals from
solutions is predominantly performed by using hy-
drogen. Hydrogen will reduce a metallic ion that is
below it in the electromotive force series, according to:
Mn+jn\2H (g) M!jnH+
#
This reaction generates hydrogen ions, which may
need to be removed to favor the reduction reaction.
Nickel and cobalt are the metals most frequently
precipitated in this way. An autoclave is required to
provide the high temperature and hydrogen partial
pressure needed for rapid reduction. Returning seed
Cementation is probably the oldest hydrometallurgi-
cal process, being used by the ancient Chinese to
produce copper at least as early as 150 BC. Chemically,
cementation involves a galvanic reaction to reduce
ions in solution. The process involves contacting the
solution with a metal that is electrochemically less
noble than that to be recovered. The less noble metal
replaces the more noble one in the solution and causes
(12) the latter to precipitate. An example is the recovery of
copper from an aqueous solution according to the
following reaction:
Cu#+jFe! Cu!jFe#+ (17)
As discussed earlier, cementation can also be used to
purify a solution. In this case, the same metal to be

5
Hydrometallurgical Principles
finally recovered from the solution is contacted with
the solution to replace the impurity in the solution. An
example is the use of zinc powder to remove cadmium
from zinc solution, according to:
Zn!jCd#+ Zn#+jCd! (18)
Commercially, the precipitant must be less expensive
than the metal to be recovered: zinc and iron are
commonly used. Aluminum would appear to be an
excellent choice, but the thin oxide layer found on
most aluminum tends to render it passive.
Metals from a solution can also be recovered in the
form of compounds such as hydroxides, sulfides, and
oxalates. An important example of metal compound
precipitation is the hydrolysis of a metal ion to form a
hydroxide precipitate. Examples include:
Fe$+j3H O Fe(OH) j3H+ (19)
# $
TiO+j2H O TiO(OH) j2H+ (20)
# # #
AlO(OH) jH O Al(OH) jOH
V V
(21)
# # $
Precipitation as sulfides by hydrogen sulfide some-
times finds application in copper and nickel metal-
lurgy. The overall reaction is given by:
M#+jH S MSj2H+ (22)
# Gupta C K, Mukherjee T K 1990 Hydrometallurgy in Extraction
Finally, crystallization of metal compounds to recover
metal values is the simplest recovery method. This
physical separation process starts with causing the
solution to attain a state of supersaturation by the
evaporation of the solvent, cooling, or the addition of
a chemical agent. Nucleation of crystals then takes
place, generally aided by the external addition of small
seed materials. The nuclei are then allowed to grow to
the desired size by maintaining a suitable degree of
supersaturation.
7. Environmental Considerations
Hydrometallurgical processes present various en-
vironmental problems. Principal concerns include the
disposal of leach residues (often acidic or basic), the
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otherwise, without permission in writing from the publishers.
rejection of sulfur and\or iron, the loss of leach
solution to the environment, the presence of toxic
impurities in solid or liquid effluents, and the need to
operate water treatment plants in order to recycle or
discharge solutions. These concerns are covered else-
where (see Metal Production : Environmental Control)
but are obviously a costly and important part of any
commercial hydrometallurgical process.
8. General Comparison of Hydrometallurgy and
Pyrometallurgy
Although the selection of metal production method is
influenced by a large number of factors, there are
certain overall characteristics that allow comparisons
between these two primary methods of metal pro-
duction. These are summarized in Table 1.
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York
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H. Y. Sohn
Encyclopedia of Materials : Science and Technology
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pp. 39763982