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MG – 4111
HYDRO-ELECTROMETALLURGY
Semester I, 2010/2011
Hydrometallurgy
Electrometallurgy
Recovery and purification of metals through
electrolytic processes by using electrical energy.
Hydrometallurgy Scope
2. Recovery
Selective precipitation of the desired metals from
a pregnant-leach solution.
General outline of hydrometallurgical
processes
Ore/concentrate
Oxidant Leaching agent
leaching
Pregnant Solution
Precipitant or
electric current
Solution purification
Precipitation
• For reaction:
aA + bB cC + dD
K
C D
a c a d
a
A = activity of A = γ[ A] →[ A] = A concentration
A B
a a a b
= activity coefficient of
component A
• Dissolution by oxidation
o RT [Fe 3+
] E = 0,77 -
8,314 x 298 [Fe 2+ ]
ln
E =E - ln [Fe3+ ]
nF [Fe 2+ ] 2x96500
[Fe2+ ]
E = 0,77 - 0,0592 log
[Fe3+ ]
E = 0,77
Vertical Line
• Reactions do not involve electron → n = 0, no
potensial , the equilibrium depends only on pH.
• Example:
At pO2 = 1 atm
At pH2 = 1 atm
Eh-pH diagram of Fe-H2O system at 25°C
Eh-pH Diagram of Zn-H2O System at 25 oC.
Eh-pH Diagram of Cu-H2O System at 25 oC.
Application of Eh – pH diagram in
hydrometallurgy
O 2 + 4H + + 4e = 2H 2 O (2)
Eo = 1.23 V.
Au 3+ / Au = 1.5
E > EO2 / H2O
O 2 / H2O = 1.23 Au 3 + / Au
2 i
in which ci = concentration of ion i in molar (mol/L)
and zi = the charge of ion i.
- It is found that activity coefficient, electrical
conductivity and the rates of ionic reactions are all
the functions of ionic strength.
Ionic Strength for unit concentration in molal
0.001ρo
I= ∑m z 2
i i
2
f
1 M s m
for salt, or
fi
i for single ion.
1 M s m
log f i 0.51159zi
2
I for single ion, and
A z z I
log f
1 Ba I
= + + -
ACTIVITY AND MEAN ACTIVITY
1/
Mean molality,
m m m
1 /
m
1 /
m
Note that m m
where
a, b, c, and d = stoichiometric coefficients of species
A, B, C, and D, respectively
k1, k2 = reaction coefficients in the forward and
reverse directions, respectively
Leaching Kinetics
• The rate expression of this stoichiometric reaction
can be written in a more general way:
1 dC A 1 dC B 1 dC C 1 dC D
- = - = = = k 1CnA CBm - k 2CpCCDq (2)
a dt b dt c dt d dt
where
CA, CB, Cc, and CD are concentrations of species A,
B, C, and D, respectively and m, n, p, q are orders of
reaction.
Leaching Kinetics
• However, if the reaction given in Eq. 1 is irreversible,
as in most leaching systems, Eq. 2 is reduced to the
following form:
1 dC A
- = k1CnA CBm
a dt
or
dC A
- = k1' CnA CBm
dt
where k1’= k1 x a.
• For this system, the rate constant, k1', and the orders of
reaction, n and m, should be determined with the aid of
leaching experimental data.
• The rate expression given in the above equations can be
further reduced if the reaction is carried out in such a
way that the concentration of A is kept constant.
• For such situations, the rate expression is reduced to:
dC A
- = k1″ CBm
dt
dC 1 dCH+
Zn2 +
= - CmZnCHn = kCHn
= k′
dt 2 dt
• If concentration of zinc metals is assumed to be constant and CH is
further abbreviated generally as CA, then the equation can be written
as follow:
dC A
- = kC nA
dt
• The order of reaction, n, can be any real number (0, 1, 2, 1.3, etc.).
• When n = 0, the reaction is referred to as “zero order” with respect
to the concentration of A.
dC A
- = kC A 0
dt
CA t
o
∫ dC A = C A - C A = k∫ dt = -kt
Co
A
0
k
or XA = t
CoA
XA
k/CAo
time
CA
ln o = -kt
CA
ln(1 - X A ) = - kt or X A = 1 - e -kt
ln (1 - XA)
k
time
For second order reaction,
CA dC A t
∫ 2 = - k ∫ dt = -kt
CA C A
o 0
XA
(1 - XA) k CAok
1 1
- = -kt
C A CoA
XA
= CoA kt
1 - XA time
k = k oe-Ea / RT
Ea 1
ln k = ln k o -
R T
Ea 1
log k = log k o -
2.303R T
Ni = - Di∇ Ci - ziμiFCi∇ Φ + Ci V
where
Ni= flux of i, Ci = concentration of i, Di = diffusion coefficient of i
Ci = concentration gradient of i, zi = valence of the specified ion,
µi = ionic mobility, F = the Faraday constant, Ф = electrical
potential gradient, and V = net velocity of the fluid of the system
First and Second Fick’s Law of Diffusion
∂ Ci
+ Di∇ 2Ci = 0 (Fick' s second law )
∂t
D
N i = (Cb - Cs )
δ
where
D = the diffusivity of the diffusing species
v = the kinematic viscosity of the fluid
L = the length of the plate
Rotating Disk.
2D
km = + 0.6Vt1/ 2 d -1/ 2 ν -1/ 6 D 2 / 3
d
μ A
Vt = 10
dρ
( )1/ 2
A = 5.0 0.66 + 0.4 log K - 5.55
4gd 3ρ(ρs - ρ)
K=
3μ2
where g is the gravitational coefficient.
Example 1:
• A cementation reaction, Zn + Cu2+ → Cu + Zn2+,
is taking place at the surface of a zinc plate of 10
cm x 10 cm area.
• Feed flowing parallel to the plate at a velocity of
1 m/s contains copper at 1 mo/dm3.
• Suppose we want to estimate the rate of
deposition assuming that the mass transfer of
Cu2+ to the zinc plate is rate determining step.
The diffusivity of Cu2+ is 7.2x10-6 cm2/s, and the
kinematic viscosity of water is 0.01 cm2/s.
1 dN Cu 2+
= k m (Cu 2b+ - Cu s2+ ) = k m Cu 2b+
S dt
where
S = the surface area of the plate
Ncu2+ = the number of moles of Cu 2+ ion
Cub2+ = the concentration of Cu2+ in the bulk
Cus2+ = the concentration of CU2+ at the interface
Example 2:
• Consider the situation from the previous example,
except that instead of a zinc plate, zinc particles 100
µm in diameter are suspended in a 1 mol/dm3 Cu2+
solution. Suppose we want to estimate the rate of
deposition of Cu2+ (Note that the density of Zn is 7.14
g/cm3.)
For particulate,
Therefore,
Vt 100.412 2.58 cm / s
Re 10 2 2.58 / 10 2 2.58
As a result ,
2 7.2 10 6
km
0.01
0.6 2.581/ 2 0.011/ 2 0.011/ 6 7.2 10 6
2/3
Finally ,
1 dN Cu 2
km 9.19 10 3 1,000 9.19 mol / cm 2 .s
S dt