03.

Electrowinning and Electrorefining in Aqueous Solution

(Zinc Electrowinning)

Pengantar Hidro-Elektrometalurgi

Wahab, S.Si., MT.

Fakultas Ilmu dan Teknologi Kebumian
Universitas Halu Oleo
 Electrowinning and electrorefining
in aqueous solution
 The following processes are performed in aqueous solution:
• Electrowinning of Zn
• Electrowinning and Electrorefining of Cu
• Electrowinning and Electrorefining of Ni and Co
• Electrorefining of Sn
• Electrooxidation of MnO2
• Electrowinning and Electrorefining of Au, Ag
Zinc Electrowinning
 Approximately 80% of world zinc production is performed
through conventional hydrometallurgical route (i.e. ZnS
roasting → ZnO calcine → leaching → ELECTROWINNING =
RLE (Roast-Leach-Electrowinning).
 The rest are done by smelting and high pressure leaching of
ZnS (without roasting).
 In addition to those produced from primary resource (ore),
zinc is also recycled from secondary resources such as from
the dust of electric furnace (EAF) for steel production
(containing 20-40% Zn), dross from hot dip galvanizing,
painting industries, slag from leadzinc smelting (containing
±10-15% Zn).
The Use of Zinc
 Raw material for hot dip galvanizing of steel
 Raw material for sacrificial anode in cathodic protection of
steel
 Raw material of brass
 Alloying elements and coating components for automotive
industris
 Chemical industries
 Painting and spray coating
 Bateries
Flow sheet of zinc production from concentrate
through RLE route:
Zinc Electrowinning
 Zinc has a standard reduction potential (Eo) = -0.763 Volt.
Thermodynamically, zinc electrowinning is difficult to be done in aqueous
solution due to hydrogen gas evolution that would be occur
simulataneously with zinc deposition on the cathode.
 Zn electrowinning can be carried out effectively by adjusting conditions so
that hydrogen overpotential (driving force for H2 evolution) is high enough
at zinc deposition potential, thus minimizing H2 gas evolution by:
− Material selection for the cathode → the kind of cathode material and
its surface roughness affect the hydrogen overpotential. Smooth
surface tends to increase the hydrogen overpotential
− Adjusting electrolyte composition
− Leach liquor purification prior to electrowinning
− Adjusting electrolysis temperature
− Adjusting currrent density
Cathode, Anode Materials and Electrowinning Tank

 The cathode is usually made of aluminium plate (Al 99.5%)

with the thickness of 5 – 7 mm and surface area of about 1
m2. Aluminium is selected, because of its high value of
hydrogen overpotential of this metal.
 The anode material is usually made of Pb-Ag alloy (0.25 –
0.75% Ag). Sr and/or Ca as well as Ti are frequently added to
improve the strength and corrosion resistance of the anode.
The surface area of the anode is usually slighty lower than
that of the cathode (± 1 m2).
 The electrolysis bath is usually made of polymer or
polymercoated concrete. Old plants still use Pb-coated
concrete.
Zn electrowinning bath
Electrolyte Composition
 Following the leaching which is done in sulphuric acid, industrial
electrowinning is carried out in ZnSO4-H2SO4 solution.
Concentration of Zn2+ ranges from 60-70 g/l and will be reduced by
time. The concentration reduce of Zn2+ is limited at 10 g/l in order
to maintain electrolyte conductivity and preventing concentration
polarisation.
 The value of hydrogen overpotential depends of several factors.
Following Tafel Equation,
h = a + b.log i
in which h = H2 overpotential, a = constant that depends on the
material and surface condition of the cathode, electrolyte
composition and temperature b = Tafel constant and i = current
density.
 Hydrogen Overpotential
• Increase by the increase of current density
• Decrease by the increase of electrolyte temperature. On
the other hand, the decrease of temperature decrease the
solution conductivity, thus increasing cell voltage and
energy consumption.
 Optimization is made by adjusting electrolyte composition,
temperature and current density.
 Process parameters that are commonly used in industries to
gain high current efficiency:
• Current densities: 400-600 A/m2, electrolyte temperature <
40oC (inlet temperature must not exceed 32oC, cooling is
required), sulphuric acid concentration 150-200 g/l.
Electrode Reaction
 Cathode : Zn2+ + 2e → Zn
 Anode : H2O → 2H+ + 1/2O2 + 2e
 Total : ZnSO4 + H2O + electrical energy → Zn + H2O + 1/2O2
 Current efficiency : 90-94%. Zinc deposit is usually stripped
after 24-28 h.
 Cell voltage : 3,3-3,5 V, energy consumption 3200-3400
kWh/tZn (3,2-3,4 kWh/kgZn)
 The presence of impurities in electrolyte solution not only
reduce the current efficiency but can also reduce the cathode
purity when it is co-deposited on the cathode.
The presence of impurities reduce current efficiency due to the
following reasons:
 The presences of impurities reduce the hydrogen
overpotential → promoting parasitic reaction of 2H+ + 2e →
H2
 Secondary reactions involving impurities ion that consumes
current, such as:
Fe3+ + e → Fe2+
occur on the cathode and its reverse of Fe2+ → Fe3+ which
occurs on the anode.
 Impurities type
a. Impurities which are more electronegative than Zn, namely Na, K,
Ca, Mg, Al, Mn → do not directly influence the electrolysis (not co-
deposited), however, when their concentrations are too high
would increase solution viscosity and reduce diffusivity Zn2+
through the diffusion layer at the cathode.
b. Impurities, which have potential in between Zn2+/Zn and 2H+/H2:
Pb, Sn, Cd → has higher hydrogen overpotential than Zn, thus, if
their concentrations are too high will be co-precipitated on the
cathode.
Fe, Co, Ni → will be co-precipitated (at high concentration) but re-
dissolved.
the concentrations of type (b) impurities are limited to be lower
than those of impurities of type (a).
 Impurities type
c. Impurities which are more electropositive than Zn and
2H+/H2 → Cu, As, Sb, In, Te, Ge → If their concentration are
too high, will be co-deposited on the cathode and due to
galvanic effect can redissolve zinc deposit.
Typical impurities concentrations allowed by zinc
Electrowinning in sulfate solution

Mn 350 mg/l Co 0,01-2 mg/l

Fe 30 mg/l As 0,01-5 mg/l
Cd 1 mg/l Sb 0,04-1 mg/l
Cu 0,5 mg/l Ge 0,002-1 mg/l
Ni 0,05-2 mg/l Se 0,02-0,1 mg/l
Te 0,001-0,005 mg/l
Zn electrowinning plant
INTEC Process for Zn Production

 Fully hidrometallurgical route to treat Zn sulphide concentrate

(without roasting).
 Main unit processes: leaching-purification-electrowinning
 The leach agent is a mixed halide species BrCl2- (HalexTM)
which is generated at the anode during electrowinning.
 Halex solution can leach Zn directly from sulphide concentrate
at atmospheric pressure (85oC)
 Purification stage consist of cementation and precipitation by
pH adjustment
INTEC Process for Zn Production

 Electrowinning stage
• Zn is electrowon from purified electrolyte which has 100
gpl Zn, 50 gpl NaCl, 50 gpl CaCl2 and 110 gpl NaBr.
• Current density 500 A/m2
• Cathode reaction : Zn2+ + 2e → Zn
• Anode raction : 2Cl- + Br- → BrCl2- + 2e
• BrCl2- patented as HalexTM is reused for leaching process
Intec Zinc Process Simplified Flow Diagram
View of a Jumbo Cathode ready for stripping of the zinc product
After removal from the Zinc Electrowinning Cell at the end of a
plating cycle. Each cathode produces up to 50 kg per day of
Special High Grade (99.99%) zinc.
INTEC Process for Zn Production

Capital cost (CAPEX)

comparison
Basis
• Plant capacity:
200,000 tpa Zn
• Zn grade in
concentrate: 50%
• Power cost 5
cent/kWh
Operating Cost (OPEX)

Cost of energy
contributes 70% of
OPEX.
Energy Consumption of
electrowinning = 3,000
kWh/tZn lower than
conventional suphate
EW ≈ 3,250 kWh/tZn.
Enviromental advantages:

 No liquid effluent
 More enviromentally friendly gaseous emission (only water
vapour no SO2)
 More stable solid residu
Thank you for your attention!
Wahab, S.Si, MT.
Fakultas Ilmu dan Teknologi Kebumian
Universitas Halu Oleo
Jl. H.E.A. Mokodompit
Kendari
INDONESIA

Telefon : +62(0)852 4193 1125

E-Mail : wahab151289@gmail.com