Hydrometallurgy

Theory and Practice

Introduction, Mining, Milling
Eberhard Krause
HydroMet Solutions Inc.
Adjunct Professor, University of Toronto

Fall 2013
Course Objectives
Provide metal-mining industry overview
Strengthen chemical engineering principles as applied to
hydrometallurgy
Provide examples of hydrometallurgical processes used
for the recovery of selected metals
Provide examples of hydrometallurgical process
equipment
Discuss challenges of the metal-mining industry
History of Metals Use
First metal use was mainly decorative, e.g. gold
jewellery
Gold and copper are malleable and can readily be
formed
Alloying of metals, e.g. bronze (Cu / Sn)
Metals used to produce household items, coinage,
weapons
Metals use expanded with onset of the Iron Age
Because of hardness and workability when heated,
better tools and weapons were produced
Development of Metals Uses
Early Environmental Concerns:
Georgius Agricola (1556)
! the strongest argument of the detractors is that the fields are
devastated by mining operations !
Also they argue that the woods and groves are cut down, for there is
need of an endless amount of wood for timbers, machines, and the
smelting of metals. And when the woods and groves are felled, then
are exterminated the beasts and birds, very many of which furnish a
pleasant and agreeable food for man !
Further, when the ores are washed, the water which has been used
poisons the brooks and streams, and either destroys the fish or drives
them away. Therefore the inhabitants of these regions, on account of
the devastation of their fields, woods, groves, brooks and rivers, find
great difficulty in procuring the necessaries of life !

Thus it is said, it is clear to all that there is greater detriment from
mining than the value of the metals which the mining produces.
Estimated Abundance of Elements in Earths Crust
Ore Formation Processes
Internal processes (magmatic, vulcanogenic)
Fractional crystallization from melts
Meteorite impact
Hydrothermal processes
Induced by hot waters containing sulfide and/or
CO
2
, e.g. hydrothermal vents
Sedimentary deposits formed under water in
reducing environments
Sudbury, Ontario Area Cu/Ni/PGM Mines
Vale
Volcanic Features of Mid-ocean Ridge
Hydrothermal vents
Heated subsurface seawater migrates through cracks in
ocean crust
Warm-water vents <30
o
C
White smokers 30
o
C - 350
o
C (white, due to
barium sulfide)
Black smokers >350
o
C (black, due to
metal sulfides; Fe, Ni, Zn)
Dissolved metals precipitate to form sulfide deposits
Unusual biological communities
Able to survive without sunlight
Archaeons and bacteria oxidize hydrogen sulfide gas to provide
food

Hydrothermal
Vents
Formation of a Uranium Ore
Finding Minerals of Commercial Value
Exploration know-how and tools
Arial photography
Area geology
Geophysical methods to find anomalies
Satellite images
Airborne magnetometers
Gravity anomalies
Seismic tomography
Ground-penetrating radar
Similarities to known ore bodies
Exploration drilling
Produce core samples for analysis
Borehole logging
Resource estimation
Tight drill spacing to gain more confidence
Exploration Drilling Core Samples
Deposit Estimation Three-dimensional Models
Expertise required by large Mining
Companies for developing New Projects
Exploration
Analytical
R&D
(Select Proc.)
Mining
Upgrading
(Milling)
Processing
(Metals
Recovery)
Sales
Engineering*
Risk Analysis
Finance, HR
Legal, !
Abandon Project ?

* Internal and External:
Pre-feasibility Study
Bankable Feasibility Study
Detailed Engineering
Tailings


Contaminated Water
Environment, Health & Safety
Decommissioning

Slags
Residues
Precipitates
Waste

Metals Occurrence in Minerals
Native metals
Au, Ag, Cu, Hg
Sulfides
HgS (cinnabar), As
2
S
3
(orpiment), AsS (realgar), FeS
2
(pyrite),
Fe
7
S
8
(pyrrhotite), CuFeS
2
(chalcopyrite), Cu
2
S (chalcocite), ZnS
(sphalerite), (Zn,Fe)S (marmatite), PbS (galena), MoS
2

(molybdenite), (Ni,Fe)
9
S
8
(pentlandite)
Carbonates
Cu
2
(OH)
2
CO
3
(malachite), Cu
3
(OH)
2
(CO
3
)
2
(azurite)
ZnCO
3
(smithsonite)
Oxides, hydroxides
Fe
3
O
4
, Fe
2
O
3
, FeO(OH) (goethite)
AlO(OH) (boehmite), Al(OH)
3
(gibbsite)
UO
2
(uraninite)
SiO
2
(quartz)
Halides
NaCl, KCl, CaF
2
Silicates
Sulfates, phosphates, molybdates, vanadates !.
Minerals used for Metals Production
Sphalerite (zincblende), ZnS
Chalcopyrite
CuFeS
2
Gold
Chalcopyrite Oxidation
Chalcopyrite
CuFeS
2
Chalcocite Cu
2
S
Covellite CuS
Azurite Malachite
Cu(OH)
2

.
CuCO
3
Cu(OH)
2

.
2CuCO
3
H
2
O, O
2
H
2
O
O
2
, CO
2
,
Massive Pentlandite Nickel Ore
Mining
Exploration
Analytical
R&D
(Select Proc.)
Mining
Upgrading
(Milling)
Processing
(Metals
Recovery)
Sales
Engineering
Risk Analysis
Finance, HR
Legal, !
Tailings



Slags
Residues
Precipitates
Waste

Mining Wikipedia Definition
Mining is the extraction of valuable minerals or other
geological materials from the earth, from an ore body,
vein or (coal) seam. The term also includes the removal
of soil. Materials recovered by mining include
base metals, precious metals, iron, uranium, coal,
diamonds, limestone, oil shale, rock salt and potash. Any
material that cannot be grown through agricultural
processes, or created artificially in a laboratory or
factory, is usually mined. Mining in a wider sense
comprises extraction of any non-renewable resource
(e.g., petroleum, natural gas, or even water).
Mining History
Historically, minerals were only found when visible
Simple equipment was used to open crevices (picks and
shovels)
Shallow depth mining
Use of horses and development of larger equipment, e.g.
water mills, pumps

Black powder (KNO
3
+ S + charcoal) first used 1627 in
mining (Slovakia)

Dynamite (nitroglycerine in absorbent) patented in 1867
Equipment sizes continue to increase, resulting in
steadily increasing productivity with respect to tonnes of
ore mined bulk mining

Ore grades are decreasing (increasing impurities)
World Mining Map
Typical Location of Oxide and Sulfide Ores
Sulfide Mining
Laterite
Open Pit Mining
4800 LEVEL
5600 LEVEL
2000 LEVEL
4000 LEVEL
6000 LEVEL
0 1000
Feet
Laterite Ore
Sulfide Ore Mining
in Hard Rock
Weathered / Oxidized Ores
Sulfide Ores
Open-pit Mining
Open-pit mining is surface mining in
which huge portions of earth are dug
from the surface to extract the desired
mineral within them. During the mining
process, the land face is scraped away
by explosives and digging creating a
deeper and deeper pit until the mining
is complete. The final shape of the
open pit is decided before excavation
begins. To most profitable mining pits
are the ones where the entire mining
area is divided into 3-D blocks. Using
geological information from drilled
holes, the value of the desired mineral
in each block is estimated. The cost of
mining each particular block is also
determined, therefore you can
designate a profit value for each block
in the mine.
from T. Paisana Open Pit Mining
Codelcos Chuquicamata (Chile) Open-pit Mine
Typical Open-Pit Mining Equipment
Bucket-wheel
Excavator
Drill-rig
Crushing and
Conveying
Shovels
Trucks
Kennecotts Bingham Canyon Mine Landslide
April 10, 2013
Nobody was hurt in the collapse of Rio Tintos Bingham Canyon open-pit mine in Utah,
the worlds largest, since workers had been evacuated following warning signs that the
ground was going to shift!
Kennecotts Bingham Canyon Mine Landslide
Typical Underground Mining Equipment
Drill
Jumbo
Loader and Dump Truck
Safety
Equipment
Confined Space
Typical Mining Costs
Open-Pit (1-3 US$ per t ore mined)
First choice if orebody is not too deep
Ore is often soft
Efficient, large-scale operation, economical for low-
grade ores
Underground (>>10 US$ per t ore mined)
Smaller scale much less efficient
Everything must pass through mine shaft or other narrow
passage
Mining for deeper, high-grade deposits, commonly in
hard rock formations
Stringent requirement for safety equipment
Structural, personal, ventilation, pumping, safe areas, etc.
Long development time - high expense
Sample Open Pit Mining Costs (2009)
Mining Costs vs. Total Operating Costs
TC/RC = Treatment & Refining Charges
~20%
~65%
Metal Production Costs
Depend on:
Scale of operation
Size of orebody
Ore grade
Tonnage of ore to be mined and treated
Location of orebody
Near surface, underground, under water
Ore mineralogy and impurities
complexity of treatment process
Safety and environmental risks
Political, social risks
Copper Production Costs
TCRC costs = Treatment Charges plus Refining Charges
It Depends !

!the only correct answer to
almost every question!

Scale of Gold Mining Operations
Barricks
Goldstrike
Operations
Micro Operators
then !. and now!
Inflationary Trends in Primary Metals
Production
Ore Upgrading (Milling)
Exploration
Analytical
R&D
(Select Proc.)
Mining
Upgrading
(Milling)
Processing
(Metals
Recovery)
Sales
Engineering
Risk Analysis
Finance, HR
Legal, !
Tailings



Slags
Residues
Precipitates
Waste

Photomicrographs of a Sulfide Ore (Sudbury)
Ccp Chalcopyrite CuFeS
2

Pn Pentlandite (FeNi)
9
S
8

Po Pyrrhotite Fe
7
S
8
Rk Rock
Mag Magnetite Fe
3
O
4
Ore Upgrading Methods
Depend on chemical properties (mineralogy) and
physical properties of ore:
Selectivity during mining
High-grading of ores
Separation by size (rejection of oversize and/or
undersize)
Crushing (in stages)
Grinding (in stages)
Classification (screens, hydrocyclones, etc.)
Gravity Separation (e.g. gold ores, chromite)
Magnetic Separation (e.g. pyrrhotite removal)
Optical sorting (e.g. diamonds)
Flotation (e.g. sulfides in flotation cells or columns)
Nickel Sulfide Ore Mineralogy and Upgrading
Major nickel mineral: pentlandite (~35% Ni), (Ni,Fe)
9
S
8

Pyrrhotite (~0.65% Ni), Fe
(1-x)
S, is the major sulfide
contaminant
If not rejected, pyrrhotite (Po) would cause high smelter slag and
SO
2
generation during smelting
Can contain up to 20% of ores nickel

Silicate gangue, popularly termed rock, and most of the
Po are rejected at the mill (flotation and magnetic
separation), producing a Ni concentrate.
Concentrates from nickel sulfide ores commonly contain
economic quantities of copper (usually as chalcopyrite),
cobalt and precious metals (Au, Ag, PGM)
Comminution: Jaw Crushers
Comminution: Roll Crushers
Comminution: Cone Crushers
Dry Classification (larger Particles)
Vibrating
Screen
Grizzly
Gyratory Screener
Ore Grindability
Depends on ore compressive strength, hardness (Mohs
scale), brittleness (ease of cleaving), elasticity
Bond method useful for determining optimal crusher and
mill type and size for particles 50 ! 0.05 mm, e.g.:
W
B
= c
B
(1/"d
E
1/"d
A
) E
F
W
B
= grinding work (kJ/kg)
c
B


= Bond grinding coefficient (Work Index)
d
A


= grain size (e.g. d
80
) of feed material
d
E


= product grain size (e.g. d
80
)
E
F
= efficiency factor

Bond Work Index determined in laboratory ball mills



Similar work indexes exist for crushing, rod mills and
smaller particles
Mohs Hardness Scale and Bond Work
Indexes for Different Materials
Effect of Mineralogy on
Grinding Efficiency
Ores contain various minerals of different
grindabilities, resulting in potential over-
grinding of some minerals, while others
remain too coarse for further processing.
Solutions:
Stage-wise (closed-circuit) grinding with
classification between stages
Fines (e.g. clay minerals) removal by washing
Basic Modes of Grinding
1
3
2
SAG (Semi Autogeneous Grinding) Mill
Rod and Ball Mills
Wet grinding most common
Stirred Media (Fine-Grinding) Mills
IsaMill
Metso Vertimill
Particle Separation by Size
and/or Density
Vibrating Screens (dry or wet)
Cone Classifiers (dry or wet)
Spiral Classifiers (wet)
Hydrocyclones (wet)
Air Classification (dry) rarely used in mining
Wet Classification Vibrating Screen
Cone Classifiers
(wet or dry)
Reichert Cone
Spiral and Rake Classifiers
Work on settling velocity differences
Move coarse particles upwards away from fines
Twin
Rake
Classifier
Centrifugal Classifiers - Hydrocyclones
Cyclone Pack
Typical Hydrocyclone
Dimensions
Particle Size Determination Techniques
Sieve Analysis
Particle sizes >37 "m (metric, ASTM, Tyler)
Laser diffraction, e.g. Malvern, Horiba
Acoustic or ultrasonic attenuation spectroscopy,
e.g. Sympatec
Image Analysis
Typical Particle Size Distributions
Bimodal Distribution
Particle Shapes SEM Images
Naturally Shaped Sands
Ground Concentrate gypsum crystals
Image Analysis e.g. Qemscan
Quantitative Evaluation of Minerals by
SCANning electron microscopy
Using backscattered electron and secondary electron signals,
in combination with electron-induced secondary X-ray emission
Particle Mapping Qemscan SEM Images
Other Ore Upgrading
Equipment
Gravity Separation for Heavy Particles,
e.g. Au, Chromite
Shaking Table
Magnetic Separation
Dry
Magnetic
Separators
Wet
Magnetic
Separator
Flotation - Principle
Separation of more hydrophobic from less hydrophobic
(or hydrophilic) materials
Separation of sulfides from gangue minerals
Separation of different sulfide minerals
Other, e.g. phosphate flotation
Differences in hydrophobicity are increased through use
of collectors (surfactants - commonly xanthates) and
other chemicals, e.g. pH and redox modifiers (e.g. lime,
H
2
SO
4
, sulfite), activators (e.g. Cu
2+
), suppressants, e.g.
dextrin, CMC (carboxy methyl cellulose), and/or
complexing agents (e.g. TETA).

The surfactant-treated hydrophobic minerals, e.g.
sulfides, attach themselves to air bubbles and are floated
to the top of reactors with the help of frothers, e.g. MIBC
(methyl isobutyl carbinol) or pine oil

OH
Collector Action - Xanthate
Potassium Amyl Xanthate (PAX) production:
R
amyl
OH + CS
2
+ KOH # R
amyl
OCS
2
K + H
2
O
R = amyl, ethyl, isobutyl
Xanthate attaches to selected mineral surfaces, e.g.
sulfides, through S atoms
Dixanthogen can form on


mineral surfaces upon oxidation
K
H
2
O
Attachment of PAX-treated Sulfides
to Air Bubbles
Mechanically agitated
Flotation Cell
Contact angle measurement
on mineral surface
Typical Grade Recovery Curve
Typical Flotation Cell Arrangement
Scavenger Cleaner Cells
Inter-stage grinding usually improves grades and/or recovery
Effect of Particle Size Distribution on
Flotation of Sulfide Ores
Flotation Example (Pb-Zn Sulfide Ores)
PbS (galena) is naturally floatable, while ZnS
(sphalerite) is not easily collected
Two-stage process (galena flotation before
sphalerite flotation):
ZnSO
4
is added in grinding to depress sphalerite during
Pb flotation at pH ~7
Sulfite and/or cyanide may be added to minimize flotation
of iron sulfides
CuSO
4
is added to activate sphalerite during Zn flotation:

ZnS + Cu
2+
! CuS + Zn
2+
(on surface)
CuS is more readily floatable than ZnS
pH raised to 10-12 to minimize flotation of iron sulfides

Photomicrographs of a Sulfide Ore (Sudbury)
Ccp Chalcopyrite CuFeS
2

Pn Pentlandite (FeNi)
9
S
8

Po Pyrrhotite Fe
7
S
8
Rk Rock
Mag Magnetite Fe
3
O
4
MAG-CLNR
SCAVENGER
Ground Feed
PYRRHOTITE
TAILS
ROCK TAILS
MAG-RCLNR
SCAV-CLNR
R - B R - A
BULK CONC
B Cleaner
Cu Rougher Cu Scavenger
Cu CONC
Vales Clarabelle Mill,
Copper Cliff, ON
Flotation rate: Ccp > Pn > Po

DETA (diethylene triamine) or TETA
(triethylene tetramine) and sulfite are
added to B Cleaner and Po
Rejection circuits.
Flotation of Pyrrhotite
Pyrrhotite oxidation may lead to formation of
elemental sulfur on the particle surfaces
Elemental sulfur is naturally floatable
Minute quantities of Cu and Ni dissolved from the
Cu / Ni minerals can activate the pyrrhotite and
make it floatable, e.g.:

FeS + Cu
2+
! CuS + Fe
2+
(on surface)
Addition of complexing agents minimizes pyrrhotite
activation

CH
2
CH
2

NH
CH
2

CH
2

Cu
NH
2

H
2
O
H
2
N
CH
2
CH
2
CH
2
CH
2

NH H
2
N NH
2

CH
2
CH
2

NH
CH
2

CH
2

Cu
NH H
2
N
CH
2
CH
2

H
2
N
CH
2
CH
2
CH
2
CH
2

NH H
2
N NH
CH
2
CH
2

NH
2

DETA TETA
CuDETA
2+

CuTETA
2+

Similar Ni-DETA and Ni-TETA complexes also exist
Mechanism of Pyrrhotite Depression involves
Complex Formation
Mechanically agitated Flotation Cells
Column Flotation
Ore
Jameson (Short) Column Cell
Roseby Copper Project
Xstrata - Raglan Concentrator
LaRonde Mineral Processing Flowsheet
Solid-Liquid Separation Processes used in
Ore Processing and Hydrometallurgy
Thickening
Traditional thickening
Clarification
Paste thickening
Filtration
Vacuum vs. pressure
Drum-, disc-, belt filter; filter press
Centrifuging
Thickener Types
Stokes Law of Sedimentation
Free Settling of spherical particles in
very dilute slurries:
Gravity force F
g
pulls particles down past
displaced liquid
At the settling velocity $, gravity force F
g

equals the drag force F
d
2 (%
p
%
f
) g r
2
$ = ------------------- for Re < 0.5
9
where $ = settling velocity


%
f
and %
p
= densities of fluid and particles


g = acceleration due to gravity


r = particle radius


= dynamic viscosity of fluid

Empirical solutions required for industrially
important Hindered Settling situations
Hindered Settling
Stokes law describes the behaviour of a single
spherical particle in an infinite fluid.
Model has limitations for practical application:
Particles are usually not spherical
Different particles in the same suspension have different
densities and particle sizes
Particle-particle interactions modify the settling behaviour
as the suspension becomes thicker hindered settling.
Semi-analytical or empirical solutions are required
for meaningful hindered settling calculations based
on simple settling tests.
Thickener Sizing - Kynch Method
A = t
u
/ h
o
c
o

A = thickener area (m
2
/ t/h)
t
u
= settling time (h)
h
o
= original pulp height (m)
c
o
= original pulp density (t/m
3
)

Settling tests for sizing
are best carried out by
equipment suppliers!

Flocculation
Polyacrylamide flocculants are added at high dilution (<0.5 g/L
in water or process solution) to hydrometallurgical thickeners
(10-100 g/t solids) to cause flocculation and thus improve the
settling rate
Cationic flocculants
Anionic flocculants
Non-ionic flocculants
Above-ground Thickeners
Deep-Cone
Settling
Pond
Paste Thickener
Applications for Paste Thickening
Mine (Paste) Backfill
Counter-current Decantation (CCD)
In-ground thickeners,
Cascading overflow
!!" $%&'()*)+ ,*-
Mlxlng 1ank
llocculanL
Make-up 1ank
Cverow
ump
underow
ump
1hlckener
!"#$% '$ ()*+,
!"#$% -.$/ ()0+,
1"#$% '$ ()0+,
1"#$% -.$/ ()*+,
!!" . /0() 1)'%0*&23 0*4 56)+789 :)&+ ")2&;*
:0<(90= 0*4 ><0?8+3
@))49)<<
/0()
A<04)2
!8<B3*
97
Top view of thickener
Notched weir design
!!" . @))49)<< ")2&;*
lmproved mlxlng and dlsslpauon of klneuc energy
Closed feedwell CFD
model http://www.cfd.com.au
Open feedwell CFD
model http://www.cfd.com.au
!!" . C*4)+789 >B3D&*;
- osluve dlsplacemenL pump requlred due Lo
hlgh slurry vlscoslLy
- Ceho, WlrLh


99
Feed Well
Turbodil

Internal Feed Dilution
Hydraulic
Rake Lift
Mechanism
Outokumpu Thickener Detail
!!" . :02% /0E8
- Wash 8auo:
- Mass rauo of CCu wash llquor Lo underow sollds
:02% /0E8 FGH I8<BJ<) K822)2 FGH
130 1.94
200 1.00
230 0.77
Impact of changes in wash ratio on soluble losses
Vacuum Filtration
Rotary Drum Filter
Horizontal Belt Filter
Automated
Horizontal
Filter Press
Pressure Filtration
Recessed Chamber Filter Press
Automated Vertical Filter Press
Filter Cloth Yarns and Weaves
Affects:
cloth tightness,
cloth elasticity,
solution flow rate
ease of filter cake release
mechanical strength
Other Common Filtration Equipment
Pressure Leaf Filter
Sand Filter
Vacuum Disc Filter
Pre-coat Pressure Disc Filter
Expertise required by large Mining
Companies for developing New Projects
Exploration
Analytical
R&D
(Process Dev)
Mining
Upgrading
(Milling)
Processing
(Metals
Recovery)
Sales
Engineering
Risk Analysis
Finance, HR
Legal, !
Tailings


Slags
Residues
Precipitates
Waste

Reagents


What is Hydrometallurgy?
Wikipedia:
Hydrometallurgy is part of the field of extractive
metallurgy involving the use of aqueous
chemistry for the recovery of metals from ores,
concentrates, and recycled or residual
materials.



Generic Hydrometallurgical Process
Final metal or compound
to market or further refining
Leaching
Metals Recovery
Purification
Ore, concentrate or
Intermediate + water
Reagents
Reagents
Effluent
Treatment
Residue +
Precipitate
Disposal
Reagents