HYDROMETALLURGY

Dr. Winny Wulandari

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 HYDROMETALLURGY

• Hydrometallurgy: concerned with the methods of production of metals and

compounds, most often from minerals but sometimes from substances produced
by another process
• The reactions occurring during sequence of process operations are implemented
in an aquatic medium
• Hydrometallurgy is by no means a competitor to pyrometallurgy; it often
combined in practice to exploit the best features both.
• Based on initial preparation, dissolution (leaching), product recovery.

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Nickel project, Western Australia (hatch.ca)

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Alumina refinery, Western Australia (Alcoa)

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 GENER AL C HA R AC TER ISTIC S OF
HYDR OMETA LLUR G IC AL PR O CESSING

• Usually carried out at < 50 oC; process streams are dilute

( < 1 mol/L of solute)
• Low temperature  Low reaction rates
• For a given throughput of metal, larger reactor volumes are
required & necessarily a larger quantity of metal is tied up
in the processing.  inventory cost
• The faster the process the smaller material hold up within
the plant & the smaller plant size.

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• High temperature hydrometallurgical processing is possible,
but must be carried out under pressure to avoid loss of
solvent.
• The size of hydrometallurgical plants are larger than of
pyrometallurgy. Equipment used in hydrometallurgical
plant are more standardized (pumps, piping, etc), & reduce
unit cost.
• To heat dilute solution need considerable amount of heat.
“low-grade” heat from pyrometallurgical process may be
utilized

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PROCESSES AIMED
AT SEPARATION
Leaching
Separation of Impurities from Solution

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 LEACHING

• Essential features:
• Valuable metal must be soluble in economically usable solvent
• Metal must be economically recoverable from solution
• Any impurity elements which are co-extracted during leaching
must be capable for further separation from solution

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 LEACHING

• Desirable features:
• Gangue minerals should not consume excessive solvent
• Solvent should be recoverable for recycle
• Feed material should be free from clay minerals
• Feed material should be porous, allowing direct contact with
solvent & phase to be dissolved
• Solvent should be non corrosive & non toxic

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 PRETREATMENT OF ORES
PRIOR TO LEACHING

• Comminution & concentration

• Comminution: fracture of the ore particles
• Concentration: particle size separation
• Chemical changes in mineral
• Carried out during pre-treatment, in most case involve
pyrometallurgical process

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 PRETREATMENT OF ORES
PRIOR TO LEACHING

• Chemical changes in minerals:

Compounds of Au, Cu, Zn, and V on the left hand side do not dissolve easily in
common reagent. CuSO4 and Na2V2O6 are water soluble. ZnO dissolves in dilute
acid solution, Au dissolves in cyanide solution

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 PRETREATMENT OF ORES
PRIOR TO LEACHING

• In some cases, the treatment are intended to make gangue

mineral less soluble to reduce reagent loss.

• By heating ore in oxygen atm, pyrrhotite is converted to

hematite. Iron oxide is insoluble in cyanide solution.

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 LEACHING TECHNIQUES

• In situ leaching: leaching of ore left in amine after it has

been worked out or the application of leach solution
directly to the ore body in the ground.

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Uranium In situ Leaching
 LEACHING TECHNIQUES

• Dump and heap leaching:

the ores, between 0.1-1 m,
is iled in dumps on a pre-
prepared impervious base.
• Typical efficiency:60%

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HEAP LEACHING

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 LEACHING TECHNIQUES

• Percolation leaching: a technique in which leach solution is

percolated through ore which has been crushed and bedded
into vats or tanks. Ores: 5-20 mm. Efficiency: 80-90%
• Fine particulate matter and clayey material must be
removed because of adverse effect to permeability.

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 LEACHING TECHNIQUES

• Agitation leaching: < 200 micron, high grade concentrates,

continuously stirred to improve rates of reaction.

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• Table 6.2.1

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 SELECTION OF LEACHING CONDITION
THE USE OF E H -PH DIAGRAM

• Relative stabilities of metals and metal compounds in aqueous solution

• First stage: identify various soluble species which may be formed in any
system
• If material do not soluble, find another system to be examined
• If metal ion can dissolve in the solution, identify range of potential of
hydrogen ion concentration / other ionic species
• pH may be adjusted by addition acid or alkali
• Potential of solution can be controlled chemically by addition of chemical
reactant or external electrical potential

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 E-PH DIAGRAM

• Pourbaix diagram: two independent variables: pH and

potential.
• Two lines on the Pourbaix Diagram represents the stability
limit for water.
• At the upperline, oxidation of water goes according to (with
oxygen at 1 atm):

• At the lower lime, reduction of water goes according to:

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ZN-WATER SYSTEM

• Zn2+ ions are

thermodynamically stable in
area X
• This implies that if any other
zinc species in the system is
exposed to condition potential
and pH in X area, it will tend
to be converted to Zn2+ species.

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EXAMPLE: ZN-H 2 O DIAGRAM
AT 25 O C

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• To obtain Zn2+ in solution:
• At low pH  acid attack to ZnO
ZnO(s) + 2H+(aq) = Zn2+(aq) + H2O

• At high pH, zinc can be obtained as ZnO22-

• Relative stabilities changes with introduction of other element to

leaching system (example: Zn-S-H2O system)
• To obtain Zn2+ from ZnS, lower pH must be used.

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 ZN-S-H 2 O SYSTEM

• Fig 6.2.6

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• Important points:
• Concentration of reactant is assumed to be constant; however, as H+ is
consumed during acid leaching of Zn2+, pH of solution will change.
Actual zinc ion concentration will depend on final pH of solution.
• In acid leaching of ZnS, new species are formed as a results of the
reaction. This will affect leaching operation  Build up of HSO4- and
SO42-
• Success of leaching operation relies on the selective reactions of
solutions with metal-bearing materials.
• Decomposition of alumina and silica is slow  selective leaching of
valuable minerals from the ore can be completed.

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 OTHER HALF REACTION:

• Oxygen must be dissolved in the solution in order to

maintain equilibrium oxygen level in the reactor.
• Other oxidators: MnO2, Fe2+, etc

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 BASE EXCHANGE REACTION.
E XA M P L E : L E A C H I N G T U N G S T E N
C O N TA I N I N G O R E S

• Conditions necessary to for leaching scheelite (CaWO 4) and wolframite

((Fe,Mn)WO4) can be determined from E-pH diagram
• The tungstates of Ca, Mn, Fe are all unstable at low pH. Decomposition
of these compounds by hydrochloric acid can be written as follows:
• MeWO4(s) + 2H+(aq)  Me2+(aq) + H2WO4(s)
• Log K = log [Me2+] + 2pH
• Log K = 7.0, 8.4, and 4.8 for Me = Ca, Mn, and Fe at 25 oC. Thus, Ca,
Mn, and Fe are taken into solution and tungsten is separated as solid
tungstic acid (H2WO4).
• Leaching at high pH is not possible: high stability of calcium tungstate

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 UTILIZING COMPLEXING IONS.
EXAMPLE: DISSOLUTION OF URANIUM
ORES

• Addition of another anionic species may be necessary for

formation of new & more soluble metal species.
• U(IV) and U(VI) in U-H2O system
• Addition of anions, such as sulphates, carbonates, nitrates
makes leaching possible through formation of stable uranyl
(VI) oxyanions :
• UO2(s) + 2H+(aq) + 0.5O2(g)  UO22+(aq)+ H2O
• Oxidising agent: oxygen, or MnO2
• MnO2(s) +2Fe2+(aq) + 4H+(aq)  Mn2+(aq) + 2Fe3+(aq) + 2H2O

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• Leaching in sulfuric acid is practiced in most cases as it is
effective : acid attack minerals as well as containing
uranium, the ore does not have to be ground so finely
• Carbonate leaching: more selective, useful for treating ores
that containing basic oxides such as CaO. Alkaline leaching
is carried out using sodium carbonate solution:
• UO2(s)+3CO32-(aq) + H2O + 0.5 H2O(g)  [UO2(CO3)3]4-(aq) +
2OH- (aq)

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 EXAMPLE: LEACHING OF GOLD

• Addition of 10-3 M sodium cyanide to the solution results

formation of stable complex Au(CN)2- :
• 2Au(s) + 4(CN)-(aq) + 2H+(aq) + 0.5O2(g)  2Au(CN2)-(aq) + H2O

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 LEACHING KINETICS

Physical Environment Chemical Environment

Rock structure Mineral compositions
-macro, faulting, cracks -Mineral associations
- micro, connected porosity - Solution chemistry: species,
Distribution of minerals concentration
Solution/gas flow -Bacterial activity
Pressure/temperature

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 LEACHING KINETICS

• Leaching of valuable mineral from ores through several

reaction steps:
• Transport of reactant in the bulk fluid to and from external
surface of ore particles
• Transport of reactants in bulk fluid through ores and fissures to
the mineral grains and residue of product layers
• Chemical, electrochemical, or biochemical reaction with the
mineral grains involving dissolution reaction and secondary
solid precipitation from solution

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• In case leaching of mineral concentrates, rates of transport
species can be increased by:
• Bulk stirring
• Increasing bulk concentration of active reagents in the solution

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 EXAMPLE: KINETICS OF GOLD
LEACHING WITH CYANIDE

• Example of effect of reactant concentration to kinetics of

leaching
• Anode: Au(s)  Au+(aq) + e
Au+(aq) + 2CN-(aq)  Au(CN)2-(aq)
• Cathode: O2(g) + 2H+(aq) + 2e  H2O2
H2O2 + 2H+(aq) + 2e  2H2O

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• For a fixed partial pressure of
O2, rate of dissolution
increases with increasing
cyanide concentration.
• Plateou rates proportional to
oxygen partial pressure
• To ensure high leaching:
solution should contain high
cyanide & high O2
concentration

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• Leaching ores particle greater
than mineral grains: particle
size & porosity are critical
factors.
• Chemical reaction rates is
generally fast compared with
mass transport processes

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 BIOLEACHING

• Many types of bacteria that can be used for leaching of

sulfide minerals. Mechanism: through a series of
electrochemical reaction.
• The presence of bacteria, acting as catalyst. Variables:
strain of bacteria present, concentrations of each type,
residence time of bacteria,
• Examples:
• Bioleaching of low-grade copper sulfide minerals
• Biooxidation of sulfidic refractory gold concentrates

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 SEPARATION OF IMPURITIES
FROM LEACH LIQUORS

• Separation from leaching:

• Lower concentration of unwanted elements in the solution, or
• Removes the desired metal selectively and leaving behind the
impurities

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 SEPARATION PROCESS

• Selective Precipitation
• Control of Potential & pH
• Thermal Precipitation
• Ion Exchange
• Liquid/Ion Exchange
• Solvent Extraction

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 SELECTIVE PRECIPITATION:
CONTROL OF POTENTIAL & PH

• The most widely used method.

• Example: at pH = 8, log(aCu2+) = -8. This results
precipitation of Cu hydroxide with only 10-8 mol of Cu2+
remaining in the solution.

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• Application: Precipitation of Cobalt Sulfide
• The separation of Nickel & Cobalt from solutions containing
ferrous sulfate is carried out using H2S.
• Equilibrium Fe, Ni, Co concentration with H2S at 1 atm: 1, 0.01,
0.00001 M respectively.
• Close control of pH allow separation of the base metal from the
solution, provide the kinetics of reaction favourable

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 SELECTIVE PRECIPITATION:
THERMAL

Altering temperature of solution  thermal precipitation.

• Application: Removal of iron ions from solution
• Fe3+ in solution, Fe3+ hydroxyl complexes are formed.
• When solution condition is changed, Fe(OH)3 forms polymers 
precipitate
•  precursor to geothite (FeOOH) or hematite (Fe2O3)
precipitation.
• High temperature, controlled addition, and good agitation can
result in the formation of geothite, magnetite, or hematite crystals.

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 ION EXCHANGE

• Metal ions in solution can exchange with specific ions

contained in a solid or second liquid phase.
• Reactions are reversible & stoichiometric, can:
• Remove unwanted ions from aqueous solution
• Increasing concentration of selected metal ions in the solution

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 LIQUID/SOLID ION EXCHANGE

• Ion exchange resins: three dimensional framework of

atoms/molecules, chemically stable.  polymeric
materials.
• Ions & regenerating reagents should be easily managed &
inexpensive.
• Example:

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 SELECTIVITY OF ION
EXCHANGE RESIN

•  Cation exchange reaction:

• RH + M+(aq) = RM+ H+(aq)
• DM : ratio of concentration of metal in the resin to in the
solution =
• When two metal ions A+ and B+ competing for adsorption
sites at the sampe pH,
• Selectivity coefficient=
• Ion exchange is an equilibrium process

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 ORDER OF SELECTIVITY

Group Order of Selectivity

-SO3H group Th4+ > Fe3+ > Al3+ > Ba2+ >
Ca2+ > Co2+> Ni2+, Cu2+ > Zn2+,
Mg2+ > UO22+ > Ag+ > Cs+ >
NH4+ > K+> H+
-COOH group H+ > Ca2+ > Mg2+ > Na+
-CH2N-(CH2COOH)2 group Hg2+ >> Cu2+ > Ni2+,UO22+ >
Zn2+ > Fe2+ > Ca2+ > Na+
-N(CH3)3OH- group SO42+ > NO3- > PO43- >
CH3COO- > I-> Br- > Cl- > F-

In general, resin prefers:

- Ion with high charge: Fe3+ > Zn2+ > Na+
- Large ions: I- > Cl- > F-
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- Ion which are poorly solvated by water: Ag+ > NH4+ > H+
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EXAMPLE: ION EXCHANGE RECOVERY
FROM URANIUM LEACH LIQUORS

• Ion exchange resin used to upgrade dilute leach liquors (0.1 – 2 g/l
solute), obtained from acid sulfate leaching of uranium deposits:
• (Extraction):
2R2SO4 + UO2(SO4)34-  R4UO2(SO4)3 + 2SO42-
• (Stripping):
R4UO2(SO4)3 + 4Cl-  4RCl + UO2(SO4)34-
• (regenerated): RCl + HSO4  2R2SO4 + 4HCl
• Extraction of anion from leach liquor carried out at pH 1-2. Resin is
washed with acidified chloride solution. Resin is regenerated by
treatment in acid solution

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 SOLVENT EXTRACTION REACTIONS
(LIQUID-LIQUID EXTRAC TION)

• Solvating reactants.
• Metals may be dissolved in organic liquirs by formation of
neutral complexes. Example:
Fe3+ + H+ + 4Cl4- = H+FeCl4-
• Iron in this neoutral complex is soluble in organic liquids
• Cation exchange reactants.
• For metal to be transferred from aqueous to organic species as
ions, must react ionically with organic reactants.
RH(organic) + M+(aq) = RM(organic) + H+(aq)

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• Chelating reactants.
• Organic molecules which form organo-metallic complexes with
specified metal ions.
• Example: reaction of extractants LIX 64, a hydroxyozime, with
copper ions to select Cu2+ ions from solutions containing Fe2+
and Cu2+.
• Anion exchange reactants
• Only one class: amines.
RNH2 + HCl = RNH3Cl = RNH3+ + Cl-

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• Solvents:
• Organic/active reactants: extractants (usually viscous)
• Inert organic carrier : diluent
• Total organic phase: solvent
• 5-10 % vol/vol is commonly used (extractant in diluent)
• Stripping:
• For recovery of metal values from organic phase
• Regeneration of the extractants for recycle

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• Stripping may be carried out as liquid/solid ion exchange.
Example:
• (load) 2RH(org) + Cu2+(aq)  R2Cu(org) + 2H+(aq)
• (strip) R2Cu(org) + 2H+(aq)  2RH(aq) + Cu2+ (aq)

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 EXAMPLE: SEPARATION OF
PLATINUM GROUP METALS
Liquid/liquid ion change techniques

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COMPOUND FORMATION

Crystallization
Chemical Precipitation of Metal Compounds

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 CRYTALLISATION

• Simplest method of removing metal from solutions as

compound

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 EXAMPLE: PRODUCTION OF
ALUMINA

• Raw material: bauxite : gibbsite (Al(OH)3), boehmite

(AlO.OH), diaspore (AlO.OH). Impurities: oxides of iron,
titanium, organic compounds
• Via Bayer Process
• Dissolution: Al(OH)3 + NaOH(aq)  NaAl(OH)4(aq)
• For gibbsitic bauxite, digestion at 140-160 C and 150 g/l NaOH
• bauxite, temp: 230-245 C, 180-200 g/l NaOH
• Diasporic bauxite, 230-280 C, 230-250 g/l NaOH

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• Alumino silicates:
Al2O3.2SiO2.2H2O(s) + 6NaOH(aq)  2NaAl(OH)(aq)
+ 2Na2SiO3(aq)
• Silica  impurities in solution
• Silica that precipitates onto iron and titanium oxides
forming waste: “red mud”
• Loss: 0.7 t NaOH and 0.86 ton Al2O3 per ton soluble silica.

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Quantumapplication.in

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• Precipitation of crystalline alumina: T = 50-85 C

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 CHEMICAL PRECIPITATION OF
METAL COMPOUNDS

• Compound formation may be carried out by addition of

chemical reagents: gases, to the solution.
• To predict optimum conditions: use Eh-pH diagram.

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METAL PRODUCTION

Cementation
Gaseous reduction
Chemical Precipitation

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 CEMENTATION

• Reduction
  of metal ions from solution by another metal is
known as cementation
• Mn+ + ne  Mo
• Reduction potential:

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 EXAMPLE: CEMENTATION OF
COPPER

• Dilute
  solution (1-2 kg/m3) of copper is contacted with metallic
iron :
Cu2+(aq) + Feo = Fe2+(aq) + Cuo

Equilibrium at 25 oC, K = 1026. Almost all copper can be removed

from solution.
Cementation  electrochemical reaction, corrosion reaction.

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 GASEOUS REDUCTION

• Gaseous
  reactants may be used to reduce metal ions in
aqueous solution.  hydrogen, H2S, SO2, CO
• Potential of hydrogen reaction:
• 2H+(aq) + 2e  H2(g)

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 EXAMPLE: REDUCTION OF NICKEL
FROM AMMINE SOLUTION

• 2+  (aq) + H2(g) = Ni(s) + 2H+(aq)

Ni

• Increasing hydrogen pressure & decreasing hydrogen ion concentration

favours the reduction of nickel ions to metal.
• Hydrogen ions may be removed by addition of NH3 to solution: H+(aq) +
NH3(g)  NH4+(aq)
• This also form complex ammine ions: [Ni(NH3)n]2+
• Two opposing effect:
• Production of nickel is favoured
• Decrease of free nickel ion concentration

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• At Sherrit-Gordon Plant, purified leach solution from
leaching Ni-Co sulfide contains 45 g/l Ni, 1 g/l Co, 350 g/l
ammonium sulfate, and free ammonia (NH3/(Ni2+ + Co2+) =
2.
• Purified solution is reacted with H2 at 36 atm & 200 oC.
• Nickel is precipitated until concentration 1 g/l, Co remains
in solution.

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 STORAGE, MIXING &
TRANSFER OF LIQUIDS

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• Bulk storage: cylindrical steel tanks
• Fluid mechanics (Re number, Fr number)
• Pumps

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 ENVIRONMENTAL PROBREMS
ASSOCIATED WITH
HYDROMETALLURGICAL PROCESSES

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 ENVIRONMENTAL PROBLEMS

• Disposal of solid leach or treatment residues: leaching

reaction may continue with natural waters
• Run-off surface waters get contamination
• Long term stability of solids must be considered
• Aqueous waste:
• That containing heavy metals must be treated with caution.
• Can be concentrated to food chains of animals & fish
• Toxicity of metals

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• Solution Purification Technologies:
• Reverse osmosis
• Ultrafiltration
• Electrodialisis

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ECONOMIC CHARACTERISTICS
OF HYDROMETALLURGICAL
PROCESSES

Leaching
Solution Purification

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 ECONOMICS: LEACHING

• Rates of leaching is slow

• Volumetric capacity of equipments is high
• Investement capital is not so great since relative simple equipments required
• Reagents (dissolved & gaseous) is conserable item in Direct Operating Cost
• Cost of increasing temperature: significant
• Least energy intensive: bacterial leaching
• Fundamental cost:
• Comminution
• Liquid/solid separation
• Residue disposal

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 ECONOMICS: SOLUTION
PURIFICATION

• Methods for removing impurities: pH change, ion-echange,

solvent extraction, crystallisation  Slow
• Size of reactants used for ion-exchange & solvent
extraction proportional to volume of liquor
• Cost of reagent: significant . Energy demand: low
• Loss of values in solution purification: minor. Typical
recovery 98-99%
• Solution purification has consequential cost on solution
generation ahead of purification

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PROBLEM EXAMPLES IN
HYDROMETALLURGY

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 WHAT IS THE BEST METHOD FOR
SEPARATING NICKEL AND COBALT?

• Question: I have a powder which is • Answer: Chemically , neodecanoic acid as

made from Co and Ni (without any extractant in a sulfate solution can be used to
other impurity). I will be appreciate if separate cobalt and nickel.
you tell me your suggestion to • Nickel, cobalt and iron(II) can be separated
separate these metals and obtain pure easily from magnesium via selective extraction
Ni and Co. using 20% Versatic 10(neodecanoic acid) as
extractant and 5% tri-n-butyl phosphate (TBP)
as phase modifier at pH 7.0,
• Answer: • Nickel and cobalt in the loaded organic phase
Cobalt and nickel both have the same  can be separated from iron(II) by selective
density, so it seems gravity separation  stripping of the two metals using 0.1 mol/L
which works based on the difference b sulfuric acid solution leaving iron(II) in the
etween density of materials is not a pr organic phase.
oper method.  93
Researchgate.com
 WHAT IS THE BEST REDUCTIVE DI
SSOLUTION WAY FOR MANGANESE
ORE (LOW GRADE)?

• One of the best way of • The best reducing agent is SO2

extracting the manganese of its in sulfuric acid medium (or
ore is hydrometallurgy method. Na2S2O5). The benefits of SO2
This process is called reductive reside in its reaction rate, the
dissolution. A lot of researchers low temperature needed, its
have worked on it and affordability and ease
suggested many reductants and purification of solutions after
solvents. I'm wondering if reduction. Its disadvantages
anyone know the best reductant are its toxicity and the
and solvent among them. constraints related to its use.

Researchgate.com 94
 COPPER (BRASS) RECOVERY F
ROM A STEEL THAT PLATED WI
TH BRASS.

• Questions: I have a • It may be possible to get the zinc with a

steel roll that plated sulphuric acid leach. The copper should stay
with behind, and the iron can be left largely
brass(copper+zinc), unaffected under the right conditions.
how can i recovery • Thermodynamics are on your side here.
Cu , Zn , steel from • The next challenge is getting the copper, while
this roll. thanks leaving the iron behind. This is more tricky.
You can try a leach with sulphuric acid and
hydrogen peroxide. You will have to control
the exposure time so that only the copper goes
into solution, while the iron remains.
• Thermodynamics are against you here, so you
Researchgate.com need to use kinetic or time barriers.
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 HOW CAN I EXTRACT PLATINU
M GROUP METALS FROM CU B
ASED ROCK?
• Imagine that I have a copper • PGMs from Cu ore are not extracted
based ore which also consists directly. They are generally extracted
only after recovery of copper by
platinum group metals. Pt , Pd, smelting-electroreffining route. The
Au, Ag are the elements in my anode slime generated in copper
Cu based ore. So how can I electrorefining contain PGMs and
extract these elements separated other metals. Several approaches are
available in literature to recover these
from each other? I am
metals step wise. Typically, anode
wondering about metallurgical, slime is subjected to decopperisation
most cost effectiveprocess and step to recover all the copper content
chemical reactions behind that and part of tellurium.
extraction. Decopperised residue udergoes
deselenisation step to recover
selenium. The deselenised anode slime
is then sujected to dore smelting and
subsequent recovery of PGMs.  96