Introduction To Hydrometallurgy - UI - Lecture Slides

Department of Metallurgical & Minerals Engineering
WA SCHOOL OF MINES
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Introduction to Hydrometallurgy
Introduction to Extractive Metallurgy
Don C. Ibana, PhD
Head of Department & Assoc Professor of Hydrometallurgy
WA SCHOOL OF MINES
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Processing Steps in Hydrometallurgy
Ore
Pre-treatment
Leaching
Solid/Liquid Separation
Leach Regeneration/
Reagent Recovery
Solution Purification/
Concentration
Metal/Product
Recovery
Residue Treatment
Tailings Disposal
Impurities
Additives for
Purification 1
2
3
4
Recycle
Liquor
Makeup
Reagent
PLS
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Pre-treatment Processes
1. Roasting of auriferous pyrite (600
o
C)
porous and insoluble Fe
2
O
3
2. Segregation roasting (600
o
C)
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Pre-treatment Processes
3. Reductive roasting of ilmenite (900
o
C)
4. Pug-roasting (100-200
o
C)
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Leaching
1. Water solvation dissolution of naturally soluble
salts in water
2. Acid attack use of acid to form a soluble salt
of the metal oxide
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Leaching
3. Alkali attack dissolution with a base (alkali)
4. Complexation formation of a complex ion
(often involves redox reactions)
Examples:
, , , ,
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Leaching
Redox reactions in leaching processes
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Leaching
Reduction of oxygen

Industrially important cathodic reactions (reduction)

O
2
+ 4H
+
+ 4e
-
2H
2
O 1.23 V (6a)
O
2
+ 2H
2
O + 4e
-
4OH
-
0.40 V (6b)
Fe
3+
is a weaker oxidant than O
2
but concentration can be increased!

Reduction of ferric ion

Fe
3
+ e
-
Fe
2+
0.77 V (7)
ln
o
RT
E E Q
nF
-
Redox reactions in leaching processes
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Complete Leaching Processes
1. Leaching of gold (redox-complexation)
O
2(g)
+ 2H
2
O
(l)
+ 4e
-
4OH
-
(aq)
Au
(s)
Au
+
(aq)
+ e
-

Au
+
(aq)
+ 2CN
-
(aq)
Au(CN)
2
-
4Au + 4CN
-
+ O
2
+ 2H
2
O

4Au(CN)
4
-
+ 4OH
-

4NaCN
(s)
4Na
+
(aq)
+ 4CN
-
(aq)
H
2
O
(aq)
+ CN
-
(aq)
HCN
(g)
+ OH
-
CaO
(s)
+ H
2
O
(l)
Ca
2+
(aq)
+ 2OH
-
(aq)
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2. Leaching of uranium
3. Leaching of nickel laterite (Caron Process)
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4. Leaching of chalcopyrite
5. Leaching of zinc sulfide 200
o
C in H
2
SO
4
with air
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6. Leaching of nickel sulfide (Sheritt Gordon Process) 105
o
C
in NH
3
with air (8 atm)
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Stability constants and Leaching Selectivity
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More
stability
constants
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Leaching Techniques
1. In-situ ore shattered by explosive, leach
solution is percolated, pregnant liquor stream
(PLS) collected through network of sumps and
pumped to the surface for purification, e.g. Cu &
U (~50% dissolution)
2. Dump/heap leaching fractured rock (0.1 1 m) is
removed from the mine, heap is built on plastic lining,
PLS collected through network of sumps and pumped to
purifying plant, e.g. Cu & U (~60% dissolution).
WA SCHOOL OF MINES
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Leaching Techniques
3. Percolation leaching ore coarsely crushed (5-
20 mm) and charged into large vats with false
bottom; lixiviant fed counter-current (80%
dissolution), Cu, Au, U.
4. Slurry (or pulp) leaching finely milled ore (200
m) is agitated (low or high turbulence) &
aerated (pressurised or open) in vessels (up to
99%).
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4. Solution Purification & Concentration
4.1 Impurity removal
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Solution Purification & Concentration cont...
Reduction potentials - (useful in reagent selection)
Au
3+
+ 3e
-
Au
0
1.41 V

Cu
2+
+ 2e
-
Cu
0
0.34 V

Ni
2+
+ 2e
-
Ni
0
-0.24 V

Cd
2+
+ 2e
-
Cd
0
-0.40 V

Fe
2+
+ 2e
-
Fe
0
-0.44 V

Zn
2+
+ 2e
-
Zn
0
-0.76 V

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Hydroxide Precipitation
Cr
3+
(aq) + 3OH
-
Cr(OH)
3
(s)
Fe
3+
(aq) + 3OH
-
Fe(OH)
3
(s)
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Solubility Product Constants Guide on Selective Precipitation
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Solubility Product Constants (Hydroxides)
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Solubility Product Constants (Sulfides)
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Use of solubility product constants (K
sp
)
A good guide on determining the solubility of an ionic solid in
water.

3
3
OH Fe
- +
sp
K
Example
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Sample calculation
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4.2 Concentration selective extraction of the valuable
metal ions from the pregnant liquor stream (PLS) into
another medium for further processing.
4.2.1 Ion-exchange (IX)
Solid
(resin)
solution Solid
(resin)
solution
immobile mobile immobile mobile
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IX Technology
manhole
water inlet
brine distributor
ion-exchange material
graded gravel underbed
treated water outlet
collecting system
brine inlet
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Step 3 - Stripping
Step 1 - Extraction
Barren
electrolyte
Recovered
extractant
Loaded
extractant
Electrolyte
MR
n
+ nH
+
nRH + M
n+

Extractant
Loaded
Extractant
PLS Raffinate
M
n+
+ nRH

MR
n
+ nH
+

Step 2 - Scrubbing
4.2.2 Solvent Extraction (SX) selective transfer of valuable
from the PLS to an immiscible organic phase using an
extractant.
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Types of Extractants
Type Functional Group Application
Chelating
R - C - C - R (oximes)
HON OH
Cu, Ni
Acidic
RCOOH (carboxylic), (R)
2
POOH (phosphinic),
R
2
PSSH (dithiophosphinic),
Cu, Co, Ni, Zn
Basic
1
o
, 2
o
amines U, Th, rare earths
3
o
, 4
o
amines U, Mo,
Solvating
Phosphoric ester (RO)
3
P=O (TBP) U, Zr/Hf,
Phosphine sulphide (R
3
P=S) Ag/Cu, Pt/Pd
Phosphine oxide (R
3
P=O), (TOPO) U
Ketones Au, Hf/Zr
Ethers Au
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Some Extraction Reactions
R
OH N OH
+
Cu
2+
R
O N OH
Cu
R
O N
+
2H
+
HO
2
Chelation
Ion exchange
P
O
OH (C
8
H
17
)
(C
8
H
17
)
+ M
2+
P
O
(C
8
H
17
)
(C
8
H
17
)
O
+ 2H
+
2
M 2
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SX Technology (Mixer-Settler)
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SX Technology (Pulse column)
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5.0 Metal/Product Recovery
5.1 Cementation
Further purified by electrorefining or pyrometallurgy.
5.2 Gaseous reduction
Sherritt Gordon Process 200
o
C, elevated H
2
pressure
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5.3 Electrowinning
Reduction of the metal ion, e.g. Cu
2+
, Ni
2+
, Zn
2+
, Co
2+
Most expensive but highest purity

5.4 Hydrolysis/Precipitation
Cooling (160 to 100
o
C) with seeding of the digestion liquor in the Bayer
Process

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5.4 Hydrolysis/Precipitation
Blowing steam into the sulfate solution increases K of the reaction &
acidity favouring hydrolysis

Blowing steam into the NH/NH
4
+
solution of Ni
2+
in Caron Process
leads to recovery of Ni(OH)
2
and NH
3
.

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35
6.0 Electrowinning & Electrorefining
Electrowinning is recovery of metal from solution;
electrorefining is refining of impure metal.
Competing cathodic reactions are
Main cathodic reaction is reduction of metal
(s)
(g) (aq)
n
M n M +
- +
e
(aq)
2
(aq)
3
Fe e Fe
+ - +
+
(s) 2
(g) (aq) H n 2H +
- +
e
(l) 2
(aq)
(aq) 2
O H 2 e 4 H 4 O + +
- +
i(l) (aq)
n
i
M ne M +
- +
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Electrowinning & Electrorefining cont...
Competing anodic reactions

Main anodic reactions
(g)
n
(aq) (s)
n M M
- +
+ e
- + +
+ e Fe Fe (aq)
3
(aq)
2
- +
+ e n M M (aq)
n
(s) i
Electrorefining
- +
+ + e H O 4 4 O 2H (aq)
) g ( 2 (l) 2
Electrowinning
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Electrowinning & Electrorefining cont...
In acidic electrowinning, anode is usually lead alloy with
small amount of antimony and silver. A protective PbO
forms and O
2
evolution occurs on oxide layer
In basic electrowinning (gold), anode is stainless steel.
Cathodes are either starter sheets of the metal to be
reduced or stainless steel (permanent).
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Periodic Table

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THE END

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Department of Metallurgical & Minerals Engineering

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