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A OF
TUDY O F IINTEGRATED LEACHING
NTEGRATED L AND
EACHING A N D ELECTROWINNING
ELECTROWINNING
OF C
OF COPPER
O P P E R FFROM CHALCOPYRITE
ROM C H A L C O P Y R I T E ORE
ORE
USING
U CHLORIDE
SING C H L O R I D E MEDIA
MEDIA
bby
y
Prashant K
Prashant Kumar
u m a r Sarswat
A thesis submitted
A submitted to the faculty
faculty of
of
The
T University of
h e University of Utah
in partial fulfillment of
partial fulfillment requirements for
of the requirements for the degree
degree of
of
Master
Master of
of Science
Science
Department
Department of
of Metallurgical
Metallurgical Engineering
Engineering
The University of
of Utah
Utah
May
M a y 2010
2010
Copyright ©
Copyright © Prashant
Prashant K
Kumar Sarswat 2010
u m a r Sarswat
of a thesis submitted by
This thesis has been read by each member of the following supervisory conunittee and
by majority vote has been found to be satisfactory.
z reb w{O
Sivaraman Guruswamy
�
THE UNIVERSITY OF UTAH GRADUATE SCHOOL
Jan D. Miller
Chair
arles MWight
Dean of The Graduate School
ABSTRACT
Hydrometallurgical recovery of copper from chalcopyrite ore using chloride media has
several advantages over sulfate based processes: faster kinetics; high solubility of metals; easy
oxidation of sulfides; reduced energy consumption step due to utilization of one electron per
atom of copper formation, rather than two in most electrowinning operations; and conversion
from water hydrolysis to ferric ferrous half-cell reaction, which reduces cell voltage.
Disadvantages include corrosivity and reduced limiting current density during electrowinning.
concentrate in chloride media may be advantageous. Several chloride media have been
examined for copper extraction. Cupric chloride and ferric chloride solutions have already
proven to be efficient leaching agents; ferrous chloride has been utilized for copper production
by means of the Hunt and Douglas process. Cupric/cuprous ion ratio plays a vital role for
leaching kinetics. Individually, ferric and cupric ions have proven to be good leaching agents; a
combination of ferric/ferrous and cupric/cuprous ions has been explored in this research by
explored in this study as a way to reduce processing and energy costs. Electrowinning has been
performed using a solution similar to that being utilized for leaching; factorial design
experiments were also conducted to study various factors which affect electrowinning.
3 2 2
In summary, this study is focused on determining the effects of Fe +, Fe +, Cu +, Cu+ and
acid concentration on leaching of chalcopyrite as well as the electrowinning of copper from the
------ - ----- --
resulting leaching
resulting leaching solution using a chloride m
solution using medium.
edium. A lab scale design of
A of experiments
experiments for
integrated leaching
integrated leaching and electrowinning
electrowinning of
of copper
copper from
from ore is discussed. Possible variations
variations of
of
electrowinning of
electrowinning copper from
of copper from chalcopyrite ore leaching
chalcopyrite ore leaching solution using chloride
solution using chloride m
media
e d i a is much
much
feasible w
when and cupric ion concentrations
h e n acid and Mi l and
concentrations are low (0.05 M/l and 0.01 Mil,
M/l, respectively).
vv
TABLE
T OF
ABLE O F CONTENTS
CONTENTS
ABSTRACT
A B S T R A C T ............................................................................................................................ .iv
iv
LIST O
LIST OF TABLES
F T A B L E S .................................................................................................................. viii
ACKNOWLEDGEMENTS
A C K N O W L E D G E M E N T S .................................................................................................... .ix
ix
Chapter
Chapter
1. IINTRODUCTION
N T R O D U C T I O N .................................................................................................. 11
1.1 Overview of
Overview of fundamental
fundamental of
of metal
metal leaching
leaching .. " ........................................... 11
1.2
1.2 Overview of
Overview of fundamental
fundamental ofof metal
metal electrowinning
electrowinning ...................................... 22
1.3
1.3 Overview of conventional chalcopyrite processing ...................................... 66
Overview of conventional chalcopyrite processing
1.4
1.4 Overview of
Overview of sulfide
sulfide based
based and
and chloride
chloride based
based media
media
for copper electrowinning
for copper electrowinning ................................................................... 88
1.5
1.5 Overview
Overview ofofleaching
leaching of chalcopyrite ore
of chalcopyrite with use
ore with use of
of
iron chlorides and copper chlorides
iron chlorides and copper chlorides ....................................................... 10
10
2. E
EXPERIMENTAL PROCEDURES
XPERIMENTAL P R O C E D U R E S .................................................................................. 12
2.1 List of
of chemicals used ........................................................................ 12
2.2 Leachant
Leachant composition
composition ........................................................... '" .......... 13
2.3 Electrochemical
Electrochemical cell and instrumentation
instrumentation ................................................ 13
2.4 Experimental
Experimental procedures .................................................................... .14
14
2.4.1 Column
C o l u m n leaching experiments with electrowinning ............................ .14 14
2.4.2 Factorial design column leaching experiments ................................ .16 16
2.4.3 Factorial design electrowinning
electrowinning experiments .................................. 20 20
2.4.4 Electrowinning test matrix II. II ..................................................... 22
22
2.4.5 Image analysis ..................................................................... .24 24
2.5 Detailed leaching kinetics evaluation ..................................................... 24 24
3. RESULTS
R E S U L T S AND
A N D DISCUSSION
D I S C U S S I O N ....................................................... '" ........ 27
27
4.
4. CONCLUSIONS
C O N C L U S I O N S ..... .. . .. ... .... .......... .. ........ ... ... . ........ .. .. .... .... ...... ........ .... .. . .73
Appendices
Appendices
A.
A. IIMAGES OF EELECTROPLATED
M A G E S OF L E C T R O P L A T E D SSAMPLES
A M P L E S . . ..... .. ........... .......... ...... .. . . ... . .... .75
B. CONCENTRATION
C OF
ONCENTRATION O IONIC SSPECIES
F IONIC P E C I E S ........ .... .......... . .. .. .... . ... .. . .. ..... ...... ..78
C. EXPERIMENTAL
E XPERIMENTAL A AND
N D SSIMULATED CURRENT
IMULATED C U R R E N T DENSITY
DENSITY
AND
A CURRENT
ND C U R R E N T PPOTENTIAL
OTENTIAL RRELATIONSHIP
ELATIONSHIP F FOR DIFFERENT
OR D TESTS
IFFERENT T E S T S ........... 84
REFERENCES
R E F E R E N C E S ........ ........ . ... .. ..... . . ...... .. .. .. .. .. . . .... . . .......... . ...... . .................... .87
vii
Vll
LIST O
LIST OFF TABLES
TABLES
Table
Table Page
22.1:
.1: Leaching solution
Leaching solution details
details for
for combined
combined leaching
leaching and
and E
EW tests ................. ... ....... 16
W tests
I would
would like to express my
m y smcere
sincere gratitude to my
m y parents for their indefatigable
indefatigable
support throughout m
support throughout my My
y education. M y deepest
deepest thanks my
thanks are due to m mother Manorama
y mother M a n o r a m a Sharma
Sharma
members,
m Prof S. Guruswamy,
e m b e r s , Prof Guruswamy, and Prof
Prof H. Y. Sohn. I gratefully acknowledge financial
gratefully acknowledge financial
to Karen
Karen Haynes
Haynes and Kay
Kay Argyle
Argyle for excellent
excellent support; to Aphichart
Aphichart Rodchanarowan
Rodchanarowan for his
also acknowledge
acknowledge the excellent
excellent support of the m
support of members of the Corrosion
e m b e r s of Corrosion Lab, specifically
specifically
Soumya My
Soumya Kar. M of gratitude
y deep sense of gratitude is for m
myy sister V
Veena
e e n a Sharma for mental
Sharma for mental support.
support.
Thanks my
Thanks to all m y colleagues lIT Kanpur
colleagues in IIT Kanpur w
who helped and
h o helped and encouraged
encouraged m pursue higher
mee to pursue
Thanks my
Thanks to m wife Shachi
y wife Shachi for mental
mental encouragement.
encouragement. I am forever grateful to all of
forever grateful of the
instructors w
who have guided
h o have my
guided m way
y w during m
a y during myy studies and
and to the Metallurgical
Metallurgical Engineering
Engineering
Department.
Department.
CHAPTER
C H A P T E R 11
IINTRODUCTION
NTRODUCTION
Tn chapter, different
In this chapter, different aspects
aspects of leaching of
of leaching of chalcopyrite
chalcopyrite ore and
and simultaneous
simultaneous
electrowinning of chloride
electro winning are discussed. Use of chloride m
media
e d i a for recovery
recovery of
of copper
copper is also reviewed.
application
application is analyzed. Conventional
Conventional methods of recovery
methods of recovery of
of copper
copper from
from chalcopyrite
chalcopyrite are
also discussed. A
Ann overview of chloride
overview of chloride based recovery and
based recovery and sulfate based recovery
sulfate based recovery of
of copper
copper
chlorides and
chlorides and copper
copper chlorides
chlorides is discussed.
discussed.
1.1 Overview
Overview of
of fundamental of metal leaching
fundamental of leaching
Leaching can be
Leaching can be defined
defined as a technique
technique bby which removal
y which removal of material can be
of material be done by
by
dissolving it away
dissolving away from
from solids. In conventional leaching [3], the solid
conventional leaching generally a
solid is generally
dissolved in an organic
dissolved organic solvent. T
The most ccommonly
h e most used extractant
o m m o n l y used extractant is hydroxyphenyl
hydroxyphenyl oxime
oxime
ions in the aqueous phase will attach to the extractant, thereby loading
loading the extractant. A
A
phase separation
phase between aqueous and organic phase
separation between phase occurs next. The
T h e aqueous phase is
stripped of
stripped of copper
copper ions, and it is called raffinate. The
called raffinate. T h e raffinate
raffinate is sent back
back to the leaching
leaching
process. Copper
Copper in the loaded
loaded organic m
medium
e d i u m is stripped
stripped into lean
lean electrolyte to make
m a k e it rich
copper
copper [4]. T h e extraction
The extraction and stripping
stripping of
of copper
copper from
from solutions with oxime
oxime solvent
solvent
extractant
extractant can be expressed as equation
be expressed equation [1.1] and [1.2].
Loading: 2+
2RH(or ) + Cu (aq) <H> R Cu(or ) + 2 H
g 2 g
+
[1.1 ]
[1.1]
Stripping: 2CU(org)) +
R 2Cu(or g+ 2H+
2H H 2RH(or ) +
^ 2RH(org) + Cu
+
C u 2+(aq) g
2+
[1.2]
1.2
1.2 Overview
Overview of
of fundamental
fundamental of
of metal electrowinning
electrowinning
electrolytically [3].
electrolytically When
W h e n metal bearing
bearing solution is kept inside the electrochemical
electrochemical cell
under applied
under positive metal ions attract toward
applied voltage, positive toward the cathode
cathode and are reduced
reduced into
into
counter balance
To counter balance the electrons for whole system, another
another reaction, oxidation, occurs on the
anode. As most
most of
of electrowinning
electrowinning occurs on aqueous media, typical oxidation reaction is
oxidation reaction
hydrolysis of
hydrolysis of water
water [3]. The
T h e two half-cell
half-cell reactions can be
be written
written as equation
equation [1.3] and [1.4].
M n +
+ ne" <r+ M [[1.3]
1.3]
3
2 H 0 «-> 0
2 2
+
+ 4 H + 4e~ [1.4]
Net reaction
Net reaction can be written as equation
b e written equation [1.5].
4M n +
+ 2nH 0 2 n 0 + 4nH + 4M
2
+
[[1.5]
1.5]
Electrowinning
Electrowinning can bbe understood by
e understood b y the diagram shown
shown in Figure 1.1.
1.1,
Anode(+)
~ H,O
Figure
F i g u r e 1.1: Schematic
S c h e m a t i c diagram
d i a g r a m of
of the
t h e ccopper
o p p e r electrowinning
e l e c t r o w i n n i n g process.
process.
4
Noow
N w consider following electrochemical
consider the following written as equation
electrochemical reaction, written equation [1.6]:
X p +
+ ne- Xm+ [1.6]
The
T h e associated electrochemical rate of
associated electrochemical reaction can
of reaction can bbee written
written as equation
equation [1.7]
FE (\-<f>)zFE
iz =
= kbC +nF exp
k C x nr
b x
exp(_f/Jz__ ) -k
m+
-C k t C x nt
nF exp
exp (- _(l_----'cp_)_ZF_E_)
f x
[1.7]
111
\ RT
RT ) 1'+ RT
RT
Using transition
Using transition state theory
theory from chemical kinetics it is possible
from chemical possible to relate the free
free energies
energies of
of
k =k exp(-*% )
f b T
[1.8]
[1.8]
m
bulk concentration
are bulk of species X
concentration of X m +
+ and X P+;; z is nnumber
and X p +
u m b e r of electrons transferred
of electrons transferred in the
constant, ~G is
constant, AG is energy
energy of
of activation and T
activation and T is
is temperature.
temperature. T
The term ¢
h e term reflects
</> thethe
reflects sensitivity
sensitivity
of the transition
of transition state to the applied If ¢
applied voltage. If <f>= =
0, 0,then
thenthethetransition
transitionstate
stateshows
showsnono
potential in a manner
potential in manner half
half w
way between the reactants
a y between reactants and products response.
and the products
This reaction
reaction provides
provides current
current density
density for
for one
one half-cell
half-cell reaction. Complete
Complete
[1.9].
5
X p +
+ Y m +
X m +
+Y p +
[1.9]
The
T cathodic reaction
h e cathodic reaction current density of
current density half-cell reaction
of the half-cell reaction must
must bbee equal
equal to the
opposite of
opposite reaction that
of the reaction that occurs anodically
anodically [3]. For
For m
more than one
o r e than one anodic
anodic and
and cathodic
cathodic
can be
can be written
written as equation
equation [1.10].
r.
S i cathodic
cathodic =
-r.
" S i i anodic
anodic [1.10]
At equilibrium
At of electrons,
equilibrium there is no net flow of electrons, even though forward
even though and backward
forward and backward reactions
FE / )
. =
i0
10 b C ^ n F ^(</Jz %/RT
= kkbC xlII+nFexp F
y k T =Ck r ^C xp+
f n FnFexp
^ (-(I-¢)
- ^ i
/ZFE/
X
) )
/RT z F E
R T
[1.11]
[U1]
the electrochemical
Hence, the electrochemical rate of reaction can
of reaction can bbee written
written as equation
equation [1.12].
i = i. [[1.12]
1.12]
where
where 11
n is overpotential.
overpotential.
function of
function of solution
solution and interfacial resistances, current
interfacial resistances, current and overall area. It is also a function
overall area. function
6
rather than
rather than free energy. T
free energy. The applied voltage
h e applied voltage can
can bbee expressed
expressed as equation
equation [1.13].
~V appli ed = ~ V half cells +~ V cathodic overpotential + ~ V anodic overpotential + IR solution + IRother [1.13]
of all process
details of process and
and related
related electrochemical If several reactions take place
electrochemical potentials. If
simultaneously
simultaneously at the electrode, a partial
partial electrode
electrode current
current density jk can be
density jk be assigned
assigned to each
individual reaction.
individual reaction. T
The partial current
h e partial current density depends on
density depends on the
the stoichiometry
stoichiometry of the reaction
of the reaction
and on
and on the
the amount of substance
amount of substance of
of X
X reacting
reacting (per
(per unit
unit time
time and
and per
per unit
unit electrode
electrode area)
area) in
in
reaction considered. T
the reaction The theoretical current
h e theoretical efficiency of
current efficiency of reaction, Ek, is defined
defined as the
of jjk tto
ratio of k current density
o the total current density as equation
equation [1.14].
1.3
1.3 Overview of conventional
Overview of chalcopyrite processing
conventional chalcopyrite processing
general, conventional
In general, chalcopyrite processing
conventional chalcopyrite processing can
can bbee divided
divided into two
two categories:
pyrometallurgical
pyrometallurgical and
and hydrometallurgical
hydrometallurgical methods
methods [5]. In pyrometallurgical
pyrometallurgical copper
extraction from
extraction from chalcopyrite, the ore is first
first crushed and ground
crushed and ground to the required
required size. Then,
7
:-----l------------
I
Potential Ll.Vap p Ii ed
Ll.Vh alf cells
___________________ ~ _____ l __
I Ll.V cathodic overpotential
-----1-------- -----
Figure
F i g u r e 1.2:
1.2: S Schematic
c h e m a t i c ddiagram of rrelationship
i a g r a m of e l a t i o n s h i p bbetween
e t w e e n llogarithm
o g a r i t h m of
of current
c u r r e n t density
density
and
a n d eelectrowinning
l e c t r o w i n n i n g potential.
potential.
8
8
chalcopyrite
chalcopyrite in the crushed
crushed and
and ground
ground ore is concentrated
concentrated bby
y flotation. During
During flotation,
flotation,
crushed and
crushed and ground
ground ore is mixed
mixed with
with a suitable collector. This collector
collector consists mostly
mostly of
absorbs on
absorbs on chalcopyrite
chalcopyrite particles
particles and
and in turn, surface of
tum, the surface chalcopyrite particles
of chalcopyrite particles becomes
becomes
hydrophobic particles of
hydrophobic particles collector coated
of collector coated chalcopyrite then attach to air bubbles
chalcopyrite then bubbles to produce
produce
in a furnace
furnace at 1250°C
1250°C to rremove
e m o v e the sulfur and iron
sulfur and iron bby
y oxidizing with oxygen
oxidizing it with oxygen [7]. Sulfur
Sulfur
dioxide and
dioxide iron oxide
and iron oxide are formed
formed as a result
result of
of the oxygen By
oxygen exposure. B removing sulfur
y removing sulfur
and iron
and iron in the matte
matte m
making copper matte
a k i n g process, copper matte containing
containing 50-70%
5 0 - 7 0 % Cu obtained [7].
Cu is obtained
The
T h e sulfur dioxide is typically
sulfur dioxide typically converted sulfuric acid in an acid plant
converted to sulfuric plant and the iron
iron oxide
oxide is
usually absorbed
usually absorbed into slag and discarded. This copper matte then undergoes
copper matte undergoes a converting
converting
approximately
approximately 1250°C
1250°C bby blowing oxygen
y blowing oxygen through copper matte. This process
through copper process results in a
relatively
relatively pure
pure copper
copper metal, called
called blister
blister copper, which 9 8 . 5 % copper
which contains about 98.5% copper [8].
This blister
This blister copper
copper is then
then further refined pyrometallurgically
further refined pyrometallurgically in an anode furnace
furnace followed
followed
bby
y electrorefining
electrorefining in a tank
tank house
house to obtain
obtain high
high purity
purity electrolytic
electrolytic grade copper
copper
(approximately
(approximately 999.99%
9 . 9 9 % Cu).
1.4
1.4 Overview
Overview of
of sulfate based and chloride
sulfate based chloride based
based media
for copper
for copper electrowinning
electrowinning
Copper electro
Copper winning from
electrowinning from sulfate based aqueous media
sulfate based media is the traditional and common
common
cathode sheet
cathode sheet as shown
shown in Figure 1.3. Because
Because of
of this characteristic, sheet can bbee easily
characteristic, this sheet
removed from
removed from the cathode. O
Onn the other
other hand, electrodeposits produced from
electrodeposits produced from chloride
chloride media
media
be granular. Hence
tend to be difficult to utilize traditional
Hence it is difficult traditional sheet harvesting equipment
sheet harvesting equipment for
for
mineral surface
mineral surface [10]. However,
However, it has been
been shown that chalcopyrite
shown that chalcopyrite leaching
leaching in halide
halide media
is relatively
relatively faster
faster [1
[ 1 , 2,
2, and 11]. Another
Another advantage of chloride
advantage of based leaching
chloride based leaching is reduced
electron
electron consumption.
consumption. Copper
Copper metal deposits due to reduction
reduction of
of cuprous
cuprous ion
ion in the case of
of
one electron
electron per
per m
mole of Cu
o l e of Cu in contrast electrons per
contrast to two electrons per mole
m o l e of copper w
of copper when
h e n reduced
from
from sulfate medium.
sulfate m e d i u m . Consequently, power consumption
Consequently, power consumption for electrowinning
electrowinning is less than
than that
from sulfate m
from sulfate medium.
edium. addition, reduction
In addition, reduction in
in iron
iron media
media reduces anode
anode energy
energy
requirements and
requirements eliminates acid
and eliminates acid misting
misting bby replacing water
y replacing water hydrolysis
hydrolysis with
with ferrous
ferrous
oxidation.
c C
c
A A
T A
T
T
H
H
H
Sulfate o0 H Chloride
0O
Media D
D D Media
E D
E
E
After Harvesting
After
~ III
II~· P.
III
III
~
Cathode Granular
Sheet Electrodeposits
Figure
F i g u r e 1.3: Comparison of electrodeposits
C o m p a r i s o n of e l e c t r o d e p o s i t s ffrom
r o m sulfate
sulfate and
a n d cchloride
h l o r i d e media.
media.
10
1.5 Overview of
1.5 Overview ofleaching
leaching of
of chalcopyrite with use of
chalcopyrite ore with of
iron chlorides
chlorides and
and copper
copper chlorides
chlorides
Ferric and
Ferric and cupric
cupric chloride
chloride solutions are very
very effective
effective oxidizing
oxidizing agents for leaching
leaching of
of
sulfide The
sulfide minerals. T h e CLEAR process utilizes a method
C L E A R process method of
of direct treatment of
direct treatment of copper
copper
concentrates with
concentrates with these two solutions
solutions [4]. There
There are two stages of
of leaching
leaching in a lixiviant
lixiviant
containing sodium
containing sodium chloride, iron chlorides, and
and copper
copper chlorides. The first stage leach, an
expressed as equation
expressed equation [1.15].
CuFeS2+
C u F e S + 44FeCh
2 - > CuCh
F e C l -----+
3 + 5 FeCh
CuCl +
2 + 2So
FeCl + 2S°
2 [[1.15]
1.15]
The
T h e second
second leaching
leaching stage, a reduction
reduction stage, uses chalcopyrite react with
chalcopyrite to react with cupric
cupric chloride,
CuFeS2+
C u F e S + 33CuCh
2 C u C l ------+
2 4CuCI ++ FeCh
» 4CuCl + 2S°
FeCl +
2 2So [[1.16]
1.16]
Sodium
Sodium chloride is added
added to keep cuprous
cuprous chloride
chloride in solution. T
The
h e solution
solution is electrolyzed
electrolyzed in
solution
solution is oxidized
oxidized at an insoluble
insoluble anode. Here
Here electrowinning low-energy step because
electrowinning is a low-energy because
the anode
anode oxidizes
oxidizes CuCI
CuCl to CuCh while the cathode
C u C l while
2 reduces CuCI
cathode reduces CuCl to metal at a very
very low cell
potential.
According
According to study
study shown
shown bby Hirato et al. [1-2] leaching
y Hirato leaching of
of chalcopyrite
chalcopyrite exhibits
exhibits half
half
order dependency
order on FFeCl
dependency on e C b3 concentration and it is independent
concentration and independent of FeCh
of F e C l concentration. In
2
FeCb. On
FeCl3. On the other
other hand, a study
study shown
shown bby
y Hirato et al. [1-2] concludes
concludes that
that the leaching
leaching of
of
chalcopyrite
chalcopyrite with CuCh
C u C ^ follows linear
linear kinetics
kinetics over
over an extended
extended period, followed
followed bby
y an
[CuCI]05.
05
Both reaction
[ C u C l ] . Both reaction 1 and
and 22 suggest that leaching
suggest that leaching kinetics
kinetics depends on
on cupric
cupric ion to
presence of
reaction, in presence not kknown
of all species, is not n o w n to date. Hence
H e n c e an experiment matrix is
experiment matrix
designed to study
designed study the effect of both
effect of both iron and copper
iron and copper chloride
chloride for examination
examination of
of a possible
subject of
a subject of discussion in this piece of
of research.
research.
leaching processes
leaching processes the solid
solid particles
particles are deposited
deposited on sloped, essentially
essentially impervious
impervious pads. A
leaching solution
leaching solution is sprayed
sprayed or dripped on top of
dripped on of the heap, and the solution
solution gradually
gradually
percolates through
percolates through the bed
bed ddown impervious pad.
o w n to the impervious The
T loaded or
h e loaded or "pregnant"
"pregnant" leach
inside a cylindrical
cylindrical column
column and leaching
leaching solution circulated in the column. This solution
solution is circulated solution is
of the experiments.
of The
The closed loop nature
closed loop nature of
of combined
combined column
column leaching
leaching with
such The
such processing. T leaching and electrowinning
h e leaching electrowinning conditions are examined separately by
examined separately by
EXPERIMENT
EXPERIMENTAAL
L PROCEEDURES
PROCEEDURES
chapter electrolyte
In this chapter electrolyte composition, column
column design, instrumentation,
instrumentation, electrochemical
electrochemical
other
other instrument
instrument are also discussed. Lastly, all of
of experimental
experimental procedures
procedures used in this study
are discussed
discussed in this chapter.
chapter.
2.1 List of
of chemicals used
EMD
E M D chemicals. Sodium
Sodium chloride (NaCI, M W ~ 58.44, 99%
(NaCl, MW 9 9 % purity), calcium
calcium chloride
chloride
((CaCb, MW
CaCl , M
2 W ~1l0.98,
- 1 1 0 . 9 8 , 99%
9 9 % purity), nitric acid (HN03, MW ~
(HNO3, MW ~ 63.01, assay 68-70%) and
obtained from
obtained Fisher Scientific. Hydrochloric
from Fisher Hydrochloric acid (HCI, MW
(HC1, M W ~
~ 36.46, assay 36.5-38%)
36.5-38%) was
was
obtained from
obtained from EMD
E M D Chemicals.
Chemicals.
All of
of these chemicals were used without
chemicals were without any further purification. All of
further purification. of the solutions
solutions
were prepared
were prepared using A
ASTM
S T M Type I water.
water.
13
2.2 Leachant
Leachant composition
composition
most of
In most of the experiments, the composition
composition of
of leachant
leachant and electrolyte was kept
electrolyte was
constant
constant for leaching
leaching and
and electrowinning. The main source
T h e main source of copper during
of copper during experiments
experiments was
iron chloride
iron chloride and cupric chloride
chloride were
were used. As solubility of
of CuCl
CuCl in water
water is very
very low, an
precipitation of
any precipitation of the copper from solution, although
copper from presence increases
although its presence increases the ionic
ionic
increases
increases solubility
solubility of cuprous ions.
of cuprous
All electrodeposition
electrodcposition experiments were performed
experiments were performed using
using a two electrode
electrode cell consisting
consisting of
of
a lead anode and stainless steel working electrode (Cathode). For combined
combined leaching and
electrowinning, a platinum
platinum m
mesh
e s h electrode chosen as the counter
electrode was chosen counter electrode
electrode (anode). For
potentiodynamic experiments
potentiodynamic experiments stainless
stainless steel electrodes (working), lead
lead counter
counter electrodes,
and saturated
and calomel reference
saturated calomel reference electrodes were
electrodes w e r e chosen. T
The reference electrode
h e reference electrode is an
Accumet
A Electrode from
c c u m e t Electrode Fisher Scientific.
from Fisher Scientific. The
T platinum counter
h e platinum counter electrode
electrode was obtained
from Beckman
from B e c k m a n instruments.
instruments.
software,
software, bby Princeton applied
y Princeton research) and a PCI4/750
applied research) potentiostat (operated
PCI41750 potentiostat (operated using
using virtual
AF
A ASR
FA rotator from
S R rotator Pine Instruments.
from Pine
14
2.4 Experimental
2.4 Experimental procedures
procedures
of the experimental
All of procedures used in this study are discussed
experimental procedures in detail in this
discussed In
section. These
These experimental procedures are provided
experimental procedures provided for column leaching experiments,
column leaching
factorial design
design leaching
leaching experiments, factorial design electrodeposition
electrodeposition experiments,
of
of combined
combined leaching and electrowinning
electrowinning (EW)
(EW) as shown Figure 22.1.
shown in Figure . 1 . One goal of
of this
leaching solution
leaching solution (after passing through
(after passing through an ore column)
column) is utilized
utilized for electrowinning.
electrowinning.
Leaching solution
Leaching was circulated
solution was circulated from EW
from the E tank through
W tank through the column
column (filled
(filled with
with ore), and
then returned
returned to the E
EWW tank. Chemical reaction
reaction between
between ore and solution
solution is responsible
responsible for
for
recirculating solution
recirculating solution w
was maintained at a set pH
a s maintained pH bby
y aa ppH Eh and
H controller. Eh and ppH
H of
of the
solution
solution were continuously monitored.
continuously monitored. Electrowon copper w
Electrowon copper was measured bby
a s measured weight in
y weight
mesh
m electrode w
e s h electrode was chosen as the counter
a s chosen Electrowinning operation
counter electrode. Electrowinning operation was carried
out in galvanostatic
out galvanostatic mode
m o d e at 5 m
rnA.
A . Solution
Solution from
from a glass reservoir
reservoir w
was
a s circulated
circulated through
through
column, which
the ore column, which is designed
designed in such
such manner only solution
manner that only solution can pass through
through the ore
and it should
should not flow back
back towards
towards the ppump
u m p side. To ensure
ensure appropriate
appropriate flow adequate
adequate
glass beads
beads and plastic
plastic m
mesh were used.
e s h were
15
Hel to
ma n pH
Figure
F i g u r e 22.1: .1: A A schematic
s c h e m a t i c diagram
d i a g r a m showing
s h o w i n g column
c o l u m n lleaching
e a c h i n g operation
o p e r a t i o n and
and
electrowinning,
e l e c t r o w i n n i n g , simultaneously.
s i m u l t a n e o u s l y . The
T h e arrows
a r r o w s show
s h o w the
t h e direction
d i r e c t i o n ofof flow of of leaching
leaching
solution.
16
experiments were
All experiments were carried
carried out
out at room
room temperature. Consumption
Consumption of
of acid (HCI)
(HC1) was
monitored
monitored and day to day consumption was recorded.
day consumption Regular
Regular monitoring
monitoring of
of
electrodeposited copper
electrodeposited copper was also performed.
performed. T
The leaching solution
h e leaching solution composition
composition is specified
specified
Table 22.1.
in Table .1.
2.4.2 Factorial
Factorial design
design column
column leaching
leaching experiments
experiments
In order
order to explore effect of
explore the effect individual components
of individual components like acid concentration,
concentration,
concentration of
concentration of ferric and
and ferrous ion, concentration of cupric
concentration of cupric and cuprous
cuprous ion, a factorial
factorial
design of
of experiments was
experiments w Factorial experiments
a s established. Factorial experiments allow us to study
study the effect
effect of
of
components (acid
components concentration, ratio of
(acid concentration, of concentration
concentration of
of ferric and ferrous
ferrous ion, and ratio of
of
concentration of
concentration of cupric and
and cuprous
cuprous ion). In most
most of
of the factorial
factorial experiments
experiments each factor
factor has
Table
T a b l e 22.1: Leaching
.1: L solution details
e a c h i n g solution details for
for combined
c o m b i n e d lleaching
e a c h i n g and EW
and E W tests
Parameter
Parameter Details
Details
Constituents
Constituents 1.9M CaCh,
1.9M C 0.1M CuCh,
a C l , 0.1M
2 CuCl , 2
Mass
M of ore
a s s of 500 gram
gram
Size of
of ore - 1 4 ++ 35) mesh
((-14 mesh
Volume
V of solution
o l u m e of 1000
1000 ml
ml
ppH of solution
H of solution 1.5
1.5
Flow rate
Flow 2.8 liter/hour
liter/hour
17
2 levels (high and low). This will result in 8 treatment combinations. A set of
of tests that
follow factorial
follow factorial design
design approach with variables
approach with Band
variables A, B and C tested
tested at high
high (+) and low (-)
presented in
levels is presented in Table 2.2
2.2.. The
T h e value of main effect
of main effect parameter
parameter and interaction
interaction effect
effect
parameter is indicative
parameter indicative of
of hhow
o w strong individual
individual factor
factor affects response variable.
affects the response variable. T
The
h e null
outcome
outcome indicates neutrality of
indicates the neutrality of effect parameter. T
effect parameter. The
h e relative effects
effects of
of the parameters
parameters
are shown
shown below:
(A) = (-Yi+ Y - Y + Y - Y + Y - Y
2 3 4 5 6 7 +Y )/8 8
(B) = (-Y1-Y2 + Y + Y - Y - Y + Y + Y ) / 8
3 4 5 6 7 8
(C) = (-Y,- Y - Y - Y + Y + Y + Y + Y ) / 8
2 3 4 5 6 7 8
Table
T Three-factor
a b l e 2.2: T h r e e - f a c t o r ddesign of experiments
e s i g n of e x p e r i m e n t s aatt high
h i g h and low levels
a n d low
Run
R un A
A B C
C AB
A B AC
A C BC
B C ABC
A BC Observation
Observation
" 11 - - - + + + - Y,
Yj
2 +
+ - - - - +
+ +
+ Y
Y22
3 - +
+ - - +
+ - + Y
Y33
4 +
+ +
+ - +
+ - - +
+ Y
Y44
55 - - + + - - +
+ Y
Ys5
6 + - +
+ - +
+ - - Y
Y66
77 - +
+ +
+ - - +
+ - Y
Y77
8 + + + + + + + Ys
Y 8
18
(AB) = (Yi+ Y - Y - Y - Y - Y + Y
2 3 4 5 6 7 +Y )/8 8
(AC) = ( Y i - Y + Y - Y - Y - Y - Y + Y ) / 8
2 3 4 5 6 7 8
(BC) = (Yi+ Y - Y - Y - Y - Y + Y + Y ) / 8
2 3 4 5 6 7 8
(ABC) = (-Yi+ Y + Y - Y + Y - Y - Y
2 3 4 5 6 7 +Y )/8 8
Chalcopyrite ore of
Chalcopyrite of size (-35 +100) was taken
taken and
and wet
wet screened properly for
screened properly for removal
removal of
Ore w
fines. Ore was then dried
a s then dried for further
further use.
use. A
A small 50 ml
ml burette
burette was used
used for leaching.
2.2.
Parameters:
Size of
Size of ore -35 + 100 mesh
+100 mesh
Time
T i m e of
of leaching
leaching 2 days
days
Mass of
Mass of ore 55 gram
gram
Volume
V of leaching
o l u m e of leaching solution 200 ml
Flow of solution
Flow rate of solution 2.8 Llhour
L/hour
19
Small Column
II Glass Chamber
Figure
F i g u r e 2.2: Schematic
S c h e m a t i c diagram
d i a g r a m sshowing
h o w i n g leaching
l e a c h i n g of
of ore
o r e in
in a small
s m a l l ccolumn
o l u m n for
for tthe
h e time
time
of ttwo
of w o days.
days.
20
factorial
factorial designed
designed so as to tind
find out the effects
effects of
of individual
individual parameters. The
T h e ratio of
of cupric
cupric
ion to cuprous
ion cuprous ion, ferric to ferrous ion, and concentration
concentration of
of HCl
HC1 are chosen as factors and
amount of
the amount of copper
copper extracted (gm/gm of
extracted (gm/gm of ore) as the response variable. The
T h e ranges of
of
concentrations
concentrations were chosen based on anticipated
chosen based anticipated operating
operating parameters. The
T h e ppH
H of
of each
solution
solution was measured before and after
measured before after leaching. After completion of
After completion of leaching, solid was
filtered
filtered out from
from the column and dried. Solid
Solid leaching residue was completely
completely ground and
experiments, beaker
beaker tests were
were also performed
performed using
using similar parameter as used
similar parameter used for factorial
factorial
a beaker
beaker for 1 day. After completion of
After of leaching, ICPMS
I C P M S analysis of
of digested ore was
was
performed
performed and
and the results were use to compare with column test results.
with column
In order
order to evaluate electrowinning performance, the same solutions were used for both
electrowinning performance,
electrowinning
electrowinning and mineral
mineral leaching. This is essential to evaluate combined
combined leaching and
and
corrosion; it is an oxygen
oxygen evolving
evolving electrode. (Use of
of reusable stainless steel electrodes
electrodes
established
established earlier
earlier in the Isa process [12] allows current density to bbe
e increased
increased by
b y 10%
1 0 % over
over
previous starter
previous starter sheet technology.) The
sheet technology.) o l u m e of
T h e vvolume of electrolyte for each test was 100 ml.
21
Table
T a b l e 22.3: Factorial
.3: F design test
a c t o r i a l design test matrix
m a t r i x for
for lleaching
e a c h i n g and
a n d electrowinning
electrowinning
Test ID
Test Cu++(M)
C + +
u (M) Cu+(M)
C +
u (M) Fe+++(M)
F e (M)+ + +
Fe++(M)
F + +
e (M) HCI(M)
HC1(M)
Cu09-01FeOl-09H05
Cu09-01Fe01-09H05 0.09
0.09 0.01 0.01 0.09
0.09 0.05
CuOl-09Fe09-01H05
Cu01-09Fe09-01H05 0.01 0.09
0.09 0.09
0.09 0.01 0.05
Cu09-01Fe09-01H05
Cu09-01Fe09-01H05 0.09
0.09 0.01 0.09
0.09 0.01 0.05
CuOl-09FeOl-09HI5
Cu01-09Fe01-09H15 0.01 0.09
0.09 0.01 0.09
0.09 0.15
Cu09-01FeOl-09HI5
Cu09-01Fe01-09H15 0.09
0.09 0.01 0.01 0.09
0.09 0.15
CuOl-09Fe09-01HI5
Cu01-09Fe09-01H15 0.01 0.09
0.09 0.09
0.09 0.01 0.15
Cu09-0 1Fe09-0 1H 15
Cu09-01Fe09-01H15 0.09
0.09 0.01 0.09
0.09 0.01 0.15
The chemicals
The chemicals used
used for these
these experiments
experiments include:
1. C
CuCh. 22 H2 0
u C l . 2H 2 2. CuCI
CuCl
FeCh
3. F eCl 3 4. FeCh.4H
F e C l . 4 H2 00
2 2
5. HCI
HC1
Electrowinning operations
Electrowinning operations were
were carried
carried out
out at 40°C. T
The
h e duration of electrowinning
duration of electrowinning was
2
hours for
20 hours for each
each set. Initially, high current mA/cm
current density, 25 m A / c m was used
used for
for a short time
assist in uniform
(100 second) to assist uniform deposition
deposition for
for later time. Deposition
Deposition was carried
carried out using
2
galvanostatic current at 5 mA/cm
galvanostatic current m A / c m . The
T h e schematic diagram for this process
schematic diagram process is shown
shown in
Figure 2.3. T
Figure The of cupric
h e ratio of cupric ion to cuprous
cuprous ion, ferric ion
ion to ferrous ion and HCI
HC1
solution
solution compositions
compositions are provided Table 2.3.
provided in Table
22
Temperature Thermometer
EW
EW tank Lead anode
Lead anode
Controller
SS
SS cathode
cathode
Temperature Potentiostat
controlled bath
F i g u r e 2.3:
Figure 2 . 3 : Schematic
S c h e m a t i c diagram
d i a g r a m representing
r e p r e s e n t i n g electrowinning
e l e c t r o w i n n i n g operation
o p e r a t i o n carried o u t in a
c a r r i e d out
cconstant
o n s t a n t temperature
t e m p e r a t u r e bath.
bath.
2.4.4 Electrowinning
Electrowinning test matrix II
additive is an essential
essential constituent
constituent for the electrolyte. Additives
Additives produce
produce fine grained,
grained, pure
pure
growth in cathodes.
In m
many
a n y cases leaching
leaching solutions produce
produce Jarosite.
Jarosite. Jarosite formation
formation tends to decrease at
low pH
pH levels. Also,
Also, low pH needed to extract
p H levels are usually needed extract metals. Thus,
Thus, in order to
maintain
maintain leaching and minimize
minimize Jarosite formation
formation in leaching
leaching columns, an additional
additional
corresponding set of
corresponding of electro winning experiments were conducted
electrowinning conducted using the solution
solution
configuration
configuration shown in Table 2.4.
2.4. As solubility
solubility of
of CuCl in water
water is very low,
low, hence in these
these
experiments
experiments calcium
calcium chloride (an indifferent
indifferent salt) was added
added to produce
produce gypsum rather than
gypsum rather
23
2
((thickness = 0.06 mm)
((thickness m m ) and area (2-3 cm
and area were
c m )))) w e r e spaced
spaced 1 cm
z
cm apart; Teflon spacers were
Teflon spacers
environment,
environment, lead is used
used as the anode. The
T h e vvolume of electrolyte
o l u m e of electrolyte for each
each set was 100 ml.
for each
hours for each set. Initially
Initially high 2S m
high current, 25 A / c m 2 was
mA/cm was used
used initially
initially for
for a short
short time (100
current
current at S m A / c m 2.. 100 pppm
5 mA/cm 2
of collagen
p m of used for each
collagen glue was used each test. Chloride
Chloride salt (O.lS
(0.15 M
M
Table
T a b l e 2.4: Electrowinning test m
E l e c t r o w i n n i n g test matrix
a t r i x II
II
2 22 +
Test ID
Test Cu
C u +(M)
2 +
(M) CU+(M)
+
Cu (M) Fee 3+(M)
F 3+
(M) Fee \M)
F (M) I (mAlcm2)
z
(mA/cm )
Cu 1O-OOF eOO-OO
CulO-OOFeOO-00 0.10
0.10 0.00
0.00 0.00
0.00 0.00
0.00 S
5
CuOO-1 OF eOO-OO
Cu00-10Fe00-00 0.00
0.00 0.10
0.10 0.00
0.00 0.00 5
C u 0 0 - 1 OF
CuOO-1 0 F e l100-00
-00 0.00
0.00 0.10
0.10 0.10
0.10 0.00 5
CuOO-1 OF eOO-03
Cu00-10Fe00-03 0.00 0.10
0.10 0.00
0.00 0.10 5
CuOO-10FeOO-03
Cu00-10Fe00-03 0.00
0.00 0.10
0.10 0.00
0.00 0.03 5
CuOO-IOFeOO-01
Cu00-10Fe00-01 0.00 0.10
0.10 0.00
0.00 0.01 5
CuOO-10Fe03-00
Cu00-10Fe03-00 0.00 0.10
0.10 0.03 0.00
0.00 5
CuOO-1 OF eO 1-00
Cu00-10Fe01-00 0.00
0.00 0.10
0.10 0.01 0.00
0.00 5
CuOO-10Fe05-05 0.00
0.00 0.10
0.10 0.05 0.05 5
5
CuOS-OSFeOS-05
Cu05-05Fe05-05 0.05 O.OS
0.05 O.OS
0.05 O.OS
0.05 5
Cu02-08F eOS-OS
Cu02-08Fe05-05 0.02 0.08 0.05 0.05 55
Cu01-09FeOS-OS
Cu01-09Fe05-05 0.01 0.09 0.05 0.05 5
24
Image analysis
2.4.5 Image
different magnifications.
different Image J software
magnifications. Image used to determine
software was used determine the deposit
deposit coverage
coverage area.
A Binocular
A Binocular Stereo Z
Zoom Microscope from
o o m Microscope Amscope
from A used for lower
m s c o p e was used lower magnification
magnification
Images. An
images. A Axioskop microscope
n Axioskop microscope from
from Zeiss was used
used for
for higher
higher magnification
magnification images.
PAX-it software
PAX-it used for image
software was used image acquisition
acquisition and analysis. Percent
Percent electrodeposit
electrodeposit
coverage was
coverage w a s calculated using Image
calculated using software. The
Image J software. The process
process of
of deposit
deposit image
image conversion
conversion to
black and
black and white
white is illustrated
illustrated in Figure
Figure 2.4.
Detailed leaching
2.5 Detailed leaching kinetics
kinetics evaluation
evaluation
Leaching experiments
Leaching experiments were
were carried out for
carried out for various particle sizes to evaluate detailed
various ore particle
Leachant for
hours. Leachant for these experiments
experiments was selected
selected from
from experiments
experiments that showcd
showed the
highest recovery
highest of copper
recovery of copper after days of
after two days of leaching. of these experiments
All of experiments were
conducted at room
conducted room temperature. Solution
Solution mixing
mixing / stirring was provided
stirring was provided bby
y means of a Teflon
means of Teflon
A small
rotator. A small amount of ore as well as solution
amount of was taken
solution was taken from bath for chemical
from the bath chemical
analysis. These
These experiments were performed
experiments were performed using
using the following parameters according
following parameters according to the
Parameters:
1. Temperature: Room
R o o m temperature
temperature
2. RPM:
R P M : 2200
00
3. Mass
Mass of
of ore: 25 gram
Volume
4. V o l u m e of
of solution: 500 ml
25
D
'- Threshold GJ IQl~
~ l ~l 255
_~ _______ 1lJ 255
Figure
F i g u r e 2.4: Steps to obtain obtain a a bblack
l a c k and
and w white
h i t e iimage
m a g e bby
y uusing
s i n g iimage
mage J J software.
s o f t w a r e . The
The
image
i m a g e is ccaptured,
a p t u r e d , tthresholded,
h r e s h o l d e d , tthen
h e n converted
c o n v e r t e d to aa bblack
l a c k and
and w white
h i t e image.
image.
26
26
Rotator
Temperature
Speed
Controlled
Control
bath
Figure
F i g u r e 22.5: Schematic
.5: S c h e m a t i c ddiagram
i a g r a m rrepresenting
e p r e s e n t i n g aa sstirred,
t i r r e d , bbatch
a t c h lleaching test ssetup
e a c h i n g test e t u p uusing
sing a
constant temperature
constant temperature bath. bath.
CHAPTER 3
CHAPTER
RESULTS
R AND
ESULTS A N D DISCUSSION
DISCUSSION
copper bby
copper y combined leaching of
combined leaching chalcopyrite ore and electroplating
of chalcopyrite electroplating of
of the copper
copper extracted.
Several
Several attempts have
have already been m
already been made
a d e in the leaching
leaching of
of chalcopyrite
chalcopyrite concentrate. Most
of
of the associated
associated research
research is done using sulfate media as the leaching
sulfate media leaching solution. In the case
case of
of
sulfate media
sulfate m leaching of
e d i a leaching of chalcopyrite, it was
was ccommonly observed that
o m m o n l y observed that mineral
mineral particles
shown to be
shown be faster than sulfate
faster than media due to a reduction
sulfate media reduction of
of passivation.
Chloride solution
Chloride solution containing
containing copper forms cuprous
copper ions forms and cupric
cuprous and cupric ion
IOn complexes,
((CuCI+,
C u C l , CuCb-,
+
CuCl ~, CuCh-
2 and CuCli-)
CuCl ~ and
3 C u C l / " ) [13]. Stability
Stability of copper ions due to the formation
of copper formation of
of
expressed
expressed bby
y reactions [3.1] and [3.2].
() +
CuFeS2(s)
CuFeS 2 + 3 Cu 2+ =
S = 44 C
2 + Cu + +
+
Fee2+ +
+ F + 22 S
S°0
2 +
[3.1
[3.1]]
CuFeS s) +
CuFeS2(s)
2( [CuCl] +
+ 3 [CuClt + 11 cr = 4 [CuCl
11C1" +
[Cucht]~+ eCl +
FeCb
+ F + 2 S
3
2
2
[3.2]
28
28
Common
C sources of
o m m o n sources of free chloride ions
free chloride ions are
are N
NaCI, HCI and
a C l , HC1 and CaCl2.
CaCb. Although
Although combined
combined
leaching and
leaching and electrowinning
electrowinning is
is done
done using
using CaCl2
CaCb as
as well
well as
as N
NaaCI, Calcium chloride
C l , Calcium chloride is
is more
more
useful in
useful in preventing
preventing Jarosite
Jarosite formation
formation bby SO/-.
removing SO4
y removing ".
Hydrometallurgical extraction
Hydrometallurgical extraction of
of copper
copper from chalcopyrite bby
from chalcopyrite chloride media
y chloride media can
can be
be
explained bby
explained reactions discussed
y reactions discussed previously
previously [15]. In
In this
this type
type of
of leaching,
leaching, solution
solution is
continuously circulated
continuously circulated in
in an
an electrowinning
electrowinning chamber/reservoir.
chamber/reservoir. TThe main
he m reaction at
a i n reaction at the
electrowinning anode
electrowinning anode is described
described as equation [3
as equation .3].
[3.3].
This operation
This operation generates
generates nascent
nascent oxygen
oxygen which
which can
can oxidize
oxidize ferrous lOn to ferric
ferrous ion ferric lOn
ion
2 Fe 2 + +
+ 2 H + [O] - > 2 F e 3 +
+ H Q 2 [3.4]
The resulting
resulting ferric ion
ion can assist
assist leaching
leaching according
according to the reaction:
CuFeS + 4 F e 2
3 +
-> C u 2 + 2 +
+ 5 F e + 2S [3 .5]
[3.5]
Generated Cu294-
+ can be plated at the cathode according to the reaction:
Generated Cu can b e plated at the cathode according to the reaction:
Cu 2 +
+ 2e"^Cu° E° =
EO = 0.34 V [3 .6]
[3.6]
29
3.1.1 Consumption
Consumption of
of acid
Acid consumption
Acid consumption is high initially, and then it becomes
b e c o m e s constant after a period of
constant after of a few
few
days in most
most of
of the tests performed
performed in this study. Initial high consumption
consumption of
of acid is the
result of
of reactions near the surface
surface of
of ore particles. Initial pH
p H is kept low
low as leaching
leaching is
approaches a constant
constant value. One possible explanation formation of
explanation for this is the formation of a reaction
product layer
product surface of
layer at the surface mineral particle. Another
of the mineral Another possible
possible reason
reason is that a high
high
amount of acid is needed initially to dissolve acid soluble components. Once these
amount of these
components
components dissolve from
from the ore, very little acid is consumed. Thus the acid consumption
consumption
in Figure 3.1.
..
g
a.
E
0.6
0.5
111-
::l ~
g~ 0.4
o 0
~ E 0.3
o ra
ra ~
~ ~0.2
..ra-
E
0.1
o
o
0 2 4 6 8 10 12 14
14
Time(Days)
Time(Days)
Figure
F i g u r e 33.1:
. 1 : Cumulative
C u m u l a t i v e acid
acid consumption/gram
c o n s u m p t i o n / g r a m of
of ore
o r e is shown
s h o w n forfor combined
c o m b i n e d column
column
leaching
l e a c h i n g and
and E EWW testtest as ddiscussed
i s c u s s e d in section
section 2.5.1. The T h e composition of solution
c o m p o s i t i o n of solution is also
mentioned
m e n t i o n e d in Table
T a b l e 22.1.
.1.
30
3.1.2 Concentration of
3.1.2 Concentration of copper
copper and iron (lCPMS
( I C P M S analysis)
The results of
The of IICPMS
C P M S analysis of
of leaching
leaching solutions are shown in Figure 3.2 and Figure
Figure
33 +
1. Copper
Copper is liberated
liberated from
from CuFeS2 bby Fee -'-,, it causing increased
y F increased dissolved
dissolved copper
copper
concentration
concentration in the column
column
94-
2. Movement of dissolved copper (Cu2+) from the column to the electrowinning
2. M o v e m e n t of dissolved copper
2
(Cu ) from the column to the electrowinning
chamber which increases Cu + concentration in electrowinning chamber
chamber which increases Cu concentration in electrowinning chamber
3. Increased mass of the working electrode due to electroplating of copper
3. Increased m a s s of the working electrode due to electroplating of copper
4. Reduced copper concentration in the solution returning to the leaching column
4. Reduced copper concentration in the solution returning to the leaching column
A slow rate of increment of dissolved copper increase indicates copper electroplating is
A slow rate of increment of dissolved copper increase indicates copper electroplating is
faster than the rate of Cu2+ transfer from the column to the electrowinning chamber. It can
faster than the rate of Cu transfer from the column to the electrowinning chamber. It can
also be assumed that the total iron is the sum ofFe 3+ and Fe2+ ions. There is likely a lowering
also be assumed that the total iron is the sum of Fe and Fe ions. There is likely a lowering
in concentration of ferrous ion and increase of concentration of ferric ions. Concentration
in concentration of ferrous ion and increase of concentration of ferric ions. Concentration
increase of iron in electrowinning chamber might be due to increase in concentration of
increase of iron in electrowinning chamber might be due to increase in concentration of
ferrous ion (ferric ion assisted leaching).
ferrous ion (ferric ion assisted leaching).
Cumulative recovery of
Cumulative recovery of electrowon
electrowon copper
copper is represented
represented in Figure 3.4. As 6.3 grams of
of
initially dissolved
initially dissolved copper recovered within 6 days. It can bbe
copper was recovered e observed
observed that the rate of
understood bby
can be understood y the fact
fact that
that rate of
of recovery
recovery depends on copper
copper dissolved
dissolved in solution.
solution.
Initially amount of
Initially the amount of copper
copper is high and subsequently
subsequently it decreases
decreases as copper
copper is being
being
-0
E
...R015
IV
0.0078
•
-...
O)
E
E
IV
TO
0.0076
—
s
~
O
'0
]g
Q)~
2 0.0074
> 0o
0
0.0074 •
I/)
I/)
'0 0.0072
...
Q)
a.
Q-
a.
Q-
0O
U
o 0.007 •
0 2 3 4 5 6 7
Time of
of leaching
leaching (days)
Figure
F i g u r e 3.2: Concentration
C o n c e n t r a t i o n ofof copper
c o p p e r (gram/gram
( g r a m / g r a m ofof ore) for for combined
c o m b i n e d lleaching
e a c h i n g andand
electrowinning
e l e c t r o w i n n i n g test. The T h e composition
c o m p o s i t i o n of of solution
solution is m mentioned
e n t i o n e d in TableT a b l e 2.1.
2 . 1 . The
The
experiment
experiment w wasa s carried
c a r r i e d out
o u t at
a t rroom
o o m ttemperature
e m p e r a t u r e and
a n d average
a v e r a g e rate
r a t e of
of electrowinning
e l e c t r o w i n n i n g of
2
10 mA/cm
m A / c m •. 2
32
-o0
E
0.016
0.014 •
-
~
(0
'-
01
i_
E
0.012 •
Ui
~
0.01
E
'-
re
01-
-
3"0- 5'- Q)
- 0.008
Q) 0
~ > 0.006
0o
III
.~
"0
T3
w 0.004 •
r:::: 0.002
C
0
'-
o 0
0 2 4 66 8
Time
T i m e of
of leaching(days)
leaching(days)
Figure
F i g u r e 3.3:
3 . 3 : Concentration
C o n c e n t r a t i o n of
of dissolved
dissolved iron
i r o n (gram/gram
( g r a m / g r a m of
of ore).
o r e ) . The
T h e composition
c o m p o s i t i o n of
solution
solution is m mentioned
e n t i o n e d in Table
T a b l e 22.1.
.1.
33
1.4
1.2 •• • ••
••
1
•• • •
• •
0.8
0.6 ••
0.4
0.2
••
o
o0 5 10 15 20
Time(days)
T ime(days)
Figure
F i g u r e 3.4: Cumulative
C u m u l a t i v e rrecovery of copper
e c o v e r y of for test
c o p p e r for test as ddiscussed in section
i s c u s s e d in section 22.4.1.
. 4 . 1 . The
The
composition of solution
c o m p o s i t i o n of solution is also mentioned
mentioned in Table 2.1.
Table 2.1.
dissolved copper
initial dissolved copper is recovered
recovered within
within 6 days. T h e source of
The remaining copper
of remaining copper is the
ore.
Analysis of
3.2 Analysis of factorial
factorial design
design column
column leaching
leaching experiments
experiments
The
T pH of
h e pH leaching solution
of leaching before and after
solution before after leaching
leaching presented
presented in Figure 3.5 shows
Figure 3.5 shows a
trend. A
trend. change in pH
A large change pH is observed
observed for the solution having a low
solution having low concentration of acid.
concentration of
Potentiostatic measurements
regime. Potentiostatic carried out bby
measurements carried y Lundstrom
Lundstrom et al. suggest
suggest that the reaction
mechanism (leaching of
mechanism (leaching of chalcopyrite with chloride media) changes
chalcopyrite with between pH
changes between pH 2 and 2.25
34
34
44
3.5 o pH (before)
3
• pH(after)
2.5
J: 2
Q.
1.5
1
Test
T 10
e s t ID
FFigure
i g u r e 3.5: Comparison
C o m p a r i s o n ofof ppH H of of lleaching solution bbefore
e a c h i n g solution e f o r e aand after leaching,
n d after leaching,
ccomposition of solution
o m p o s i t i o n of solution is ppresented in TTable
r e s e n t e d in for eeach
a b l e 2.2 for test ID.
a c h test ID.
35
dissolution, which
which is normally
nonnally higher
higher at low ppH. The
H. T objective of
h e objective factorial design
of the factorial
experiment combinations of
experiment is to evaluate combinations of all indicated
indicated ionic species, mentioned
mentioned in Table
Table 22.1,
.1,
which cause m
which maximum
a x i m u m recovery of copper. Another
recovery of Another purpose
purpose of
of the factorial
factorial design
experiment is to
experiment study the effect
study of individual
effect of individual factors on the response
response variable. The
The
combination of
combination parameter showing
of parameter mImmum
showing m i n i m u m copper and iron
copper and iron concentration
concentration In
in the ore
which corresponds
residue, which maximum
corresponds to the m selected for
a x i m u m leaching, was selected for a m
more
o r e detailed
leaching kinetics
leaching kinetics study. Dreisinger
Dreisinger et al. [16] have
have already
already reported
reported enhanced
enhanced leaching
leaching in the
presence of
presence of chloride
chloride media. One of the advantages
O n e of advantages of
of chloride
chloride m
media leaching is that
e d i a leaching that there is
overpotential to oxidation
a low overpotential oxidation of
of sulfides. This low overpotential
overpotential to oxidation
oxidation is not
not
observed
observed in sulfate based leaching. Although
sulfate based Although it is hard make
hard to m a k e conclusions from various
conclusions from
because of
studies because of different
different experimental
experimental conditions, some of which
some of which are controversial, it is
likely
likely that m o r e than
more one pphenomenon
than one h e n o m e n o n is involved
involved in the inhibition of chalcopyrite
inhibition of chalcopyrite leaching.
A combination
A combination of
of ferric/ferrous ion and cupric/cuprous
ferric/ferrous ion cupric/cuprous ions might
might have a synergistic
synergistic effect
effect
fluctuation is observed
fluctuation ICP data for
observed for Iep for different
different sets of follow a
of experiments, the data follow
cuprous
cuprous ion and
and high acid quantity
high acid causes m
quantity causes a x i m u m leaching, this combination
maximum combination shows
shows
consistency for
consistency for three similar
similar tests, and hence
hence this combination
combination was chosen
chosen for a morc
more
detailed
detailed analysis. Set "0"
" 0 " represents
represents ore sample
sample without
without leaching
leaching (total copper content in ore
copper content ore
is 0.58%, which
is 0.58%, which is
is in close proximity
in close proximity to
to typical
typical low
low grade ore copper
grade ore copper content) [18].
content) [18].
According to
According to Wilson
Wilson et al.[6] the
et al.[6] the ratio of cuprous
ratio of cuprous to cupric ions
to cupric must bbe
ions must e less
less than 1.9 in
than 1.9 order
in order
36
to m
make
a k e the following reaction thermodynamically
following reaction more
thermodynamically m feasible due to stability
o r e feasible of cuprous
stability of
ions in complexes.
CuFeS2(s)
C u F e S ) + 3 [CuClt
2{s
+ 11cr
[CuCl] + 11C1" =
+
= 44 [CuChf
[CuCl ] ~ ++ FeCh 2S (~G0298
F e C l ++ 2S
3 (AG° =
2
10.4 Kcal/mol)
= lOA Kcal/mol) [3.8]
2 [3.8]
298
Maurice et al.[14]
Maurice a1.[14] proposed
proposed reaction
reaction (equation
(equation [3.9]) when
when leaching carried out
leaching is carried out bby
y using
ferric chloride.
CuFeS2(s)
CuFeS + 4 FeCI/
+ F e C l +3Cr=
2 ( s )
+
+3C1 = CuCl
2 e C l ++ 2S
CuCI + ++ 55 FFeCh +
2S 2 ((~G0298
A G ° == -16.7
298
-16.7 Kcal/mol)
Kcal/mol) [3.9]
CuFeS2(s)
CuFeS + 3 FFeCh
+ eCl =
2 ( s ) CuCl +
= CuCI + 44 F
3 FeCh + 2 S°
eCl + SO 2 [3.10]
The standard
standard free energy change of
energy change of a leaching
leaching reaction
reaction with
with ferric chloride
chloride is negative,
whereas that
whereas that with
with cupric
cupric chloride
chloride is positive. Thus
Thus under
under standard
standard conditions
conditions ferric chloride
leaching more
leaching is m feasible than
o r e feasible than cupric
cupric chloride Cupric chloride
chloride leaching. Cupric chloride leaching is
thermodynamic
thermodynamic feasible in high
high CuCI+
C u C l and cr +
When
CI" concentrations. W h e n the concentration
concentration of
of
Cu
C u + at some stage reaches 1.9
+
Cuu 2+ concentration,
1.9 times the C concentration, the free energy
2 +
change of
energy change of
to occur
occur for leaching of low
leaching of low grade ore in tests where
where the ratio of
of cuprous
cuprous to cupric ion
ion is 0.11
leaching of
leaching of ore. Hence Cu +I/ Cu
Hence the Cu 2
Cu-'- ratio factor should have
factor should have a positive
positive effect
effect over
over the
results of
of the factorial
factorial design analysis shown
shown in Table 3.1. The dissolved
dissolved copper
copper at the end
end
of
of each test is represented
represented in Figure 3.6. Hydrochloric
Hydrochloric acid is a source of
of chloride ions. Thus,
the reaction
reaction is m
more
o r e feasible at low ppH w h e n the cr
H when CI" concentration
concentration is high due to the
formation of
formation of chlorocomplexes
chlorocomplexes [15]. As expected
expected the factorial
factorial design analysis represented
represented in
The factorial
factorial design analysis utilizes copper recovered (gram/gram
copper recovered (gram/gram of
of ore) as the response
response
The
T h e factors used
used in the factorial
factorial design
design analysis are:
2
• C u + / Cu+
Variable 1 = Cu 2 +
Cu +
= factor 1
• Variable 3 = HCI
HC1 concentration
concentration = factor 3
independently statistically
independently statistically significant
significant based
based on their effect
effect on the response. The
T h e estimates of
of
(Cu2+/Cu+)
/Cu ) (ratio of
of concentration)
concentration) is changed
changed from
from low to high, the expected
expected improvement
improvement
of response
of response variable (recovery) is 0.001026. Similarly
Similarly for variable
variable (3), if
if hydrochloric
hydrochloric acid
concentration
concentration is changed
changed from
from low to high, w
wee can expect improvement bby
expect improvement y 0.001776
0.001776 with
values were
were examined. These values are compared
compared using difference
difference between
between predicted
predicted and
38
Table
T a b l e 33.1:
. 1 : Factorial
F a c t o r i a l ddesign
e s i g n analysis
analysis m matrix
a t r i x for tests as ssummarized
for tests in T
u m m a r i z e d in Table
a b l e 2.2, copper
copper
rrecovery
e c o v e r y is chosen
c h o s e n as tthe h e rresponse
e s p o n s e variable
variable
Factor
Factor Effect
Effect Standard
Standard Error F P
Meanllnterc.
Mean/Interc. 0.002688 0.000137 - -
(l)Varl
(l)Varl 0.001026 0.000274 29.64198 0.115641
(2)Var2 -0.000924
-0.000924 0.000274 13.44444
13 .44444 0.169501
1 by
b y 22 -0.000707
-0.000707 0.000274 6.53086 0.237451
1 by
b y 33 -0.000374
-0.000374 0.000274 3.56790 0.309970
2 bby
y 3 -0.000557
-0.000557 0.000274 4.45679 0.281624
-e
-...
o
o
E
III
0.007
0.006
0.005 r-- -
r-
tn
E 0.004
-
...
~
III
- -
.,
Q)
0.003 r--
r--
> 0.002
"0
I/) 0.001
.,...
I/)
o n
Q)
Q.
Q.
o
U
TestlD
Test ID
Figure
F i g u r e 3.6: C Copper
o p p e r ((gram/gram of ore) for
g r a m / g r a m of for digested
d i g e s t e d oore
r e as bbased
a s e d on
on IICP
C P analysis.
analysis.
Composition of solution
C o m p o s i t i o n of solution is presented
presented in Table
Table 2.2 for each
for e a c h test.
39
~£ 0.006
o
0.006 -r-------------------------
'0
| 0.005
E 0.005
III
~
J? 0.004
0.004
E
E
~
S 0.003
J> 0.003
1j
1~> 0.002
0.002
o>
......|~ 0.001
0.001
~
S. 0 4-~~~~~~~--~~--~~--~~--~~--~~--~-----~
ac..
o Cu01·
Cu01- Cu09·
Cu09- Cu01·
Cu01- Cu09· Cu01·
Cu09- Cu01- Cu09·
Cu09- Cu01· Cu09·
Cu01- Cu09-
u
O 09Fe01· 01 Fe01 · 09Fe09· 01 Fe09· 09Fe01· 01 Fe01· 09Fe09-
09Fe09· 01Fe09-
01 Fe09·
09Fe01- 01Fe01- 09Fe09- 01Fe09- 09Fe01- 01Fe01-
09H05 09H05 01H05
09H05 01H05 01H05
01H05 09H15 09H15 01H15 01H15 01H15
10
Test ID
Figure
F i g u r e 3.7: Copper
C o p p e r recovered
r e c o v e r e d for
for digested
digested oreo r e determined
d e t e r m i n e d bby
y ICP
I C P analysis.
analysis.
Composition
C o m p o s i t i o n of
of solution
solution is presented in Table
p r e s e n t e d in for each
T a b l e 2.2 for test ID.
e a c h test ID.
40
which is measure
which of the validity
measure of validity of The
of the result. T value ofp
h e value of p represents the decreasing
decreasing
index of
index reliability of
of reliability of the results. Only variable 3 shows
Only variable shows a value 0.078, which
which is in close
response variable
response variable can
can bbe assumed to bbe
e assumed statistically significant.
e statistically significant. Other
Other values of
of p are less
significant.
significant.
conditions
conditions differ
differ more than would
m o r e than would be expected. FF statistics values
values were calculated
calculated to test the
regime is shown
regime fonn of
shown in the form of contours.
Analysis ofleaching
3.3 Analysis of leaching experiments
experiments
Analysis of leaching
Analysis of discussed in section
leaching experiments, discussed is done for
section 2.6, IS for vanous
various
detennined
determined at different intervals bby
different time intervals y IICPMS Chemical analysis of
C P M S analysis. Chemical residual ore
of residual
0.001
0.006
• > 0.005
0.005 _ < 0.0047
004 D
~ o· 03
< 0.0040
• < 0.0037
S o·0
~
<>
_ < 0. 00 27
~ O.OOZ
01
O· 0
Figure
F i g u r e 3.8: 33D D ccontour plot for
o n t o u r plot for rrecovered
e c o v e r e d ccopper vs. different
o p p e r vs. different ffactors,
a c t o r s , bbased
a s e d oon
n output
output
of ffactorial
of a c t o r i a l ddesign
e s i g n eexperiments. Details of
x p e r i m e n t s . Details of eexperiments
x p e r i m e n t s aare
r e ppresented
r e s e n t e d inin TTable
a b l e 2.2.
42
- 3.5
:::::::
E
-...
Cl
G)
c.
3
c. -+- (-14+35) mesh
0
U ___ (-4+14) mesh
2.5 - 6 - (-270) mesh
2
o 1 2 3 4 5 6 7
Tim e (day)
Figure
F i g u r e 3.9: Concentration
C o n c e n t r a t i o n of
of Cu
C u (gmlliter)
(gm/liter) vs. ttime i m e for
for 25 grams
g r a m s of
of chalcopyrite
c h a l c o p y r i t e ore
o r e was
was
used
u s e d in 500 ml m l ofof solution
solution (Test (Test ID
I D Cu0901Fe0109H15).
C u 0 9 0 1 F e 0 1 0 9 H 1 5 ) . All experiments
e x p e r i m e n t s were
w e r e carried
carried
out
o u t for
for 144 hours
h o u r s at
a t room
r o o m temperature.
temperature.
intervals.
intervals. The
T h e goal of
of these leaching
leaching experiments
experiments was to determine the time dependent
dependent
conversion or dissolution
conversion or dissolution of
of chalcopyrite
chalcopyrite ore particles.
particles. The resulting
resulting leaching
leaching data can be
be
used to predict
predict the recovery
recovery for different
different ore particle sizes as well as to predict
predict economic
economic
viability of
viability of the operation. Data
Data obtained from ICP analyses of
obtained from of solutions can bbe
e used to
determine
determine which
which model best
best describes reaction kinetics of
of solid ore particle leaching. Two
Two
leaching
leaching models were
were evaluated using the set of
evaluated using of data.
3.3.1 Modell:
Model 1: spherical particle
particle under
under reaction
reaction control
control
This assumption
This assumption can
can be
be expressed
expressed as
as equation
equation [3.11].
tt aa l - ( l - a ) 1/3
1-(1-a) 1I3 [3.11]
[3.11]
where
where
time of
tt = time of leaching
= fraction
aa = fraction reacted
3.3.2 Model
3.3.2 Model 2: spherical
spherical particle
particle under
under product
product layer
layer control
In Model
In Model 22 an entity
entity is disseminated
disseminated within
within aa nonreactive
nonreactive matrix. Model
Model 22 also
also applies
applies to
cases in
cases in which
which product
product layer
layer is formed
formed on
on pure
pure particles.
Model 22 kinetics
Model kinetics leads
leads to:
tt a lI-3(1-a)2/3
- 3 ( l - a r + 2(I-a)
J
2(l-a) [3.12]
where t is time
where time;; a = fraction
fraction reacted
It is assumed
assumed that
that all ore particles
particles for analysis are spherical.
The
T h e fit of
of data
data to Model
Model 2 is presented
presented in Figure
Figure 3.10
3.1 0 whereas
whereas that for Model
Model 1 is shown
shown
in Figure
Figure 3.11. Data
Data in Figure 3.10
3.10 and 3.11 indicate the lowest
lowest correlation
correlation coefficient
coefficient value
contain a range of
of different
different particle sizes, whereas the leaching models
models assume monosize
monosize
particles. The
particles. T h e -4
- 4 ++14
1 4 size particles provide the best model fit for leaching by
b y the Model 2
kinetics.
44
0.3 1.2
• -270 mesh
0.25
•
--
M
N
<
nI:s
0.2
• (-4+14) mesh
~ (-14+35) mesh
Y = 0.0016x - 0.0347
R2 = 0.8078
0.8
-
"("'"
I
n:s
0.15 0.6 n:s
-
M
NI
"("'"
0.1
0.05
y=O
R2 = 0.9539
y = 5E-05x - 0.0005
0.4
0.2
R2 = 0.9647
0 • 0
0 20 40 60 80 100 120 140 160
Time(hours)
Time(hours)
Figure
F i g u r e 3.10: L Leaching
e a c h i n g pparameter
a r a m e t e r 1_3(I_a)2/3
l-3(l-a) +
+ 22(I-a)
(l-a) vs. ttime for 25 ggrams
i m e for r a m s of
chalcopyrite
c h a l c o p y r i t e oore
re w wasa s uused s e d in 500 m mll ofof solution
solution (Test
(Test ID
ID CCu0901FeOl09HI5).
u 0 9 0 1 F e 0 1 0 9 H 1 5 ) . All
experiments
experiments w were
e r e carried
c a r r i e d oout for 144 hours
u t for h o u r s at
a t rroom
o o m temperature.
temperature.
45
0.7 1.2
0.6
• -270 mesh •
• (-4+14) mesh y = 0.0042x - 0.0525 1
R2 = 0.9038
fl (-14+35) mesh
0.5
0.8
--
<
M
oor-
co
0.4
y = 0.0031x + 0.0022 0.6 co
- •
oor-
•
oor-
0.3
R2 = 0.989
0.4
0.2
y = 0.0006x + 0.0042
0.1 • R2 = 0.9913 0.2
0 0
0 50 100 150 200
Time (hours)
Figure 3 . 1 1 : Leaching
F i g u r e 3.11: L e a c h i n g pparameter"
a r a m e t e r " 1-(1-a)I/3"
l - ( l - a ) " vs. ttime i m e for
for 25 ggrams of chalcopyrite
r a m s of chalcopyrite
ore
o r e was
w a s uused
s e d in 500 m mll ofof solution (Test ID
solution (Test Cu0901FeOl09HI5).
ID C u 0 9 0 1 F e 0 1 0 9 H 1 5 ) . All experiments
e x p e r i m e n t s were
were
carried
c a r r i e d oout for 144
u t for 144 hhourso u r s at
a t rroom
o o m temperature.
temperature.
46
46
3A Analysis
3.4 Analysis of
of factorial
factorial design
design electrowinning
electrowinning Experiments
Experiments
Comparison of
3 A .l Comparison
3.4.1 of current
current efficiency
efficiency (experimental
(experimental and simulated)
simulated)
Electrowinning is carried
Electrowinning carried out using electrolytes as discussed
out using discussed in sections
sections 2.2 and 2.3. Each
electrolyte
electrolyte contains variety of
contains a variety of ionic species. The
T h e concentrations of species in this study
concentrations of
were calculated
were calculated using
using Visual
Visual Minteq
Minteq software.
software. These
These values are shown Appendix A.
shown in Appendix
Major
Major ionic species in
in the electrolyte Cu2+,, Cu
electrolyte are Cu Cu+,, CuCl
CuCb-" ,Fe 2 3
H+ ,cr
, Fe +,, Fe + , H
2 , CI" and OK
OH"
ions as well
well as from copper chloride
from copper chloride complexes. The following are the reactions
T h e following of greatest
reactions of greatest
written as:
importance, written
Cu z +
+2e" Cu [3.13]
Cu + e" Cu [3.14]
Fe 2+ [3.16]
+
2 H + e" - > H 2 [3.17]
2H 0
2
+
4H + 0 2 + 4e" [3.18]
[3.19]
47
The of weight
T h e ratio of weight of
of copper metal deposited
copper metal deposited on cathode to the theoretical
on the cathode theoretical weight
weight
obtained
obtained from Faraday's
from F Law is used
a r a d a y ' s Law used to calculate
calculate current
current efficiency, written as equation
efficiency, written equation
[3.20-3.22]
„ . .
r £
Weight of
Weight of metal
metal deposit
deposit r _
Current efficiency
Current efficiency =
= [3.20]
[3.20]
Theoretical weight obtained from Faraday's Law
Theoretical weight obtained from Faraday's Law
! . , . , Total charge
Total charge flow
flow _ _. _
where
t
where theoretical
theoretical weight
weight ==
r
[3.21]
P-21J
charge require for one mole of deposit
charge require for one m o l e of deposit
Total charge
Total charge = Current density *
Current density area *
* area time duration
* time duration of current flow
of current flow [3.22]
of the reduction
In the case of reduction reactions
reactions occurring
occurring at an electrode, the theoretical
theoretical m
mass can be
a s s can be
calculated in
calculated in the following manner (based
following manner (based on
on discussion
discussion in section
section 1.2):
1.2):
Total copper
copper in the solution
solution can be represented
can be represented as: [Cu]
Copper complexes
Copper complexes and ionic forms
forms in this study
study can
can bbee represented
represented primarily
primarily as: [Cu+],
[Cu ], +
2+
[ C u ] , and [CuCl "] 2
The concentration of
T h e total concentration of copper sum of
copper is the sum of individual
individual ionic species concentrations
concentrations and
shown in equation
shown equation [3.23].
+ 2+
[Cu] = [ C u ] + [ C u ] + [CuCl ~]
2 [3.23]
[3.23]
The
T and theoretical
h e total mass and theoretical weight can bbee expressed
weight can expressed as shown
shown bby equation [3.24].
y equation
Theoretical weight
Theoretical weight and
and total charge
charge flow are expressed
expressed as equations
equations [3.25] and [3.26],
respectively.
48
48
Mass = Total
Mass=
Total charge
charge flow
-
r
flow x[Cu +
xlCu ]/\ + [Cu ]/2 2+
2 +
11]
_ . /_2 + ^[CuCl; ],.,1
+] /.„1 + [Cu 2+]
+ [CuCl ] / l |
r _
[3 .24]
[3.24]
[Cu] x 96485 2
[Cu] x 96485
where theoretical
where weight == — — —
theoretical weight Q [3.25]
96485 .3
96485.3
= Current
0Q = Current density
density xx aarea
r e a xx time
time of
of current
current flow
flow [3.26]
For electrodeposition
For electrodeposition of
of copper
copper only,
only, reaction
reaction [3.13],
[3 .13], [3.14],
[3.14] , and
and [3.15] are
are considered
considered as
22 +
the reactions
the reactions of
of importance
importance and
and hence
hence C
Cu Cu
u +,, C and CuCk"
u + and CuCh - are
are considered
+
considered for
for reduction.
reduction.
The
T reaction involving
h e reaction involving the
the conversion
conversion of
of C
CuCI{ copper conversion
2
u C l " to copper
3 conversion is ignored
ignored because
concentration of C11CI3
concentration of CuCb 2-" is 100 times lower than the CuCh
2
CuCl "- concentration. Other complexes
complexes
2
ignored because
are ignored because of
of their
their low
low concentrations.
Experimental current
Experimental current efficiency
efficiency can
can be
be determined
determined in the
the following
following steps:
A general
A general electrochemical
electrochemical reaction
reaction can
can bbee written
written as equation
equation [3.27].
Ox +
Ox ne- -~
+ ne" > Red
Red [3.27]
"Ox"
" O x " is the oxidized form of
oxidized form of species and "Red" reduced form of
" R e d " is the reduced The
of species. T h e rate of
of
(forward reaction) =
Rate (forward = krorward
k f d [Ox] orwar [3.28]
[3.28]
Similarly backward
backward reaction can bbe
e expressed
expressed as equation [3.29]
[3.29]..
49
Rate
Rate (backward = kb
(backward reaction) = kbackward
kward [Red]
ac
[3 .29]
[3.29]
Current
Current density
density can also be
be determined using the equation
determined using equation [3.30).
[3.30].
I backward =
- ZZ F kbackward [Red] [3 .30]
[3.30]
constant.
Anodic current
Anodic current can bbe written as equation
e written equation [3.31).
[3.31].
la
ia =- F Kbackward Creduction
Creduction exp (aaFE
i c hT )
m F E [ 3 . 3 [3.31]
1 ]
where Ua a and
where a and aU c are charge transfer
c coefficients. It is often
transfer coefficients. often assumed
assumed that:
aU a +
a +Uac = 1
c
Based on
Based discussion in section
on discussion section l.2,
1.2, Butler
Butler - V
Volmer equation is written
o l m e r equation written as equation
equation [3.33).
[3.33].
50
._ .[exp(aaFl]/)
li -— -lo
—iQ IRT - exp(-acFl]/)]
exp IRT [3.33]
11
rj = E- Eo
E 0
Use
U s e of
of the Butler-Volmer equation is justified
Butler-Volmer equation justified w
when electrical current
h e n electrical current at the electrode
electrode
current no longer
current depends on potential. Instead, under
longer depends under mass
mass transport
transport control
control rate is limited
[3.34].
nFDC b
[3.34]
8
where n is nnumber
where of electrons involved
u m b e r of involved in the electrode
electrode reaction
F == Faraday
Faraday constant, D = Diffusion constant, 8 =
= Diffusion = Diffusion Cbb =
Diffusion layer thickness, C = Bulk
Bulk
concentration
concentration
A modified
A modified Butler-Volmer
Butler-Volmer equation which corrects for mass transport
equation which transport was used
used in this
study. Solution
Solution resistance
resistance is considered
considered and
and compensated.
compensated. T
The current potential
h e current potential relationship
relationship
(plot of E
(plot of E vs. log Iii), information for single as well
|i|), gives information well as multiple
multiple electrochemical
electrochemical
flow information.
information. Individual
Individual current
current can
can also determined
determined bby
y finding abscissa for each
finding the abscissa
reaction
reaction as shown
shown in Figure
Figure 3.12. Current efficiency for
Current efficiency for multiple
multiple reaction systems can be
reaction systems be
51
Reaction 3
Reaction 2
E
E
Sum ofof
reactions
---
\
Eo
E 0
\
...
log 111
III logl111
logliil log|l |2 log|l |3
Llog
H o g III
Figure
F i g u r e 3.12: Log L o g ((Current)
C u r r e n t ) vs. P Potential
o t e n t i a l ggraph
r a p h for
for aa m multielectrochemical
u l t i e l e c t r o c h e m i c a l reaction
reaction
system.
system. T Three
h r e e different
different reactions
r e a c t i o n s aare
r e cconsidered
o n s i d e r e d to demonstrate
d e m o n s t r a t e tthe h e rrate
a t e of
of reaction
reaction
calculation for iindividual
c a l c u l a t i o n for n d i v i d u a l as well
well as overall
o v e r a l l ccurrent
u r r e n t efficiency.
efficiency.
calculated
calculated by
b y adding
adding the current density for the sum
current density sum of copper reduction
of copper reduction reactions
reactions divided
divided by
by
Based
Based on
on this concept, the average
average experimental current efficiency
experimental current efficiency is calculated
calculated for three
of experiments. SIMMER
sets of S I M M E R (Simulator
(Simulator for Integrated
Integrated Metallurgical
Metallurgical and Materials
Materials
Engineering was
Engineering w a s used calculate the theoretical
used to calculate theoretical current
current efficiency.
efficiency. The
T h e software
software interface
interface
window
w i n d o w is shown
shown in Figure
Figure 3.13. This software can simulate potentiodynamic
software can potentiodynamic scan
scan results for
for
52
~ SIMMER
SIMMER (Simulator
(Simulator for
for Integrated
Integrated Metallurgical
Metallurgicaland
and Materials
Materials Electrochemical
ElectrochemicalReactions)
Reactions) GJ[Q)[gJ
f-~]f5 | X
Graph Limits
Graph Limits
Species
Species 2.5e0
Information
Information
L ogfX min
LoglX min(A/m2lJr-r--
(A/m2)) IT3LogfXLoglX m maxax(A/m2lJ
(A/m2)J J7*~
Y
Ymin min(Volts)
[volts] ~
rZ5 Ymax
Y max(Volts)
(Volts) F5"
Electrode
Electrode
Reactions
Reactions Reference Points (lNhite Squares)
Reference Points (White Squares)
log (A/m2) Y
log Iii|i|(A/m2) Y(Volts)
(Volts) loglil (A/m2)
loglil (A/m2) Y Y (Volts)
(Volts)
Experimental
Experimental
|o jo F~
10 10
Conditions
Conditions E(V)
10 10 Id
jo
10 |o
10 [5
10 lo
10
Surfactant
Surfactant !o
10 10
lo lo""'
10 |o
10
Information
|0
10 fo0
1 F~
10 ^0
10
Red
Red 11 Fe3+ ++1e-
|lFe3+ 1Fe2+
1e-= = 1Fe2+ 10
jo j-1.37e+001
1-1 .37e+001 Counter
Co unterElectrode
EIectrodeData
Data (PointslThin
(Points/ThinUne)Line)
Blue 12H+
|2H+ ++2e-2e-= 2H2(aq)
= 2H2(aq) |4.90e+000 Pot .. ntial M r;;;;-7 ~ Rate(A/m2) jinsuffic rate
.. (Alm2) linsuffic. rate
Blue |o
10 14.90e+000 Potential (V) f
Rat
Gr .... n
Green 14H+ 102(aq)+ 4e-
)4H+ ++102(aq) = 2H20
+ 4e- = 2H20 F~
10 ]-4.52e+001
1-452e+001 Cell Voltage
Voltage Cell Power
Relative to to Cell Power
y .. llow 11
Yellow CuCI2- ++1e-
j1CuCI2- 1e-= 1=Cu1Cu
+ 2CI-
+ 2CI- 10 ]4.90e-001
14.90e-001 Working Electr_
Working Density
Electr. (W/m2)
Density Open Circuit
Open Circuit
11 Cu2+ + 2e- 1 Cu Pot.
Pot_ (V) (V) Potential
PotentialM (V)
Orange |1CU2+ + 2e- = 1Cu
Orange = fo
10 J3.17e+001
13.17e+001 (W/mZ)
Purple 11
Purple Cu+ ++11e-
|1CU+ e- = =
1Cu1Cu fo
10 |3.27e-003
13. 27e-003 lout ofofrange
lout range [outof
lout of range j-0.0828
range 1-00828
Figure
F i g u r e 33.13:
. 1 3 : SIMMER
S I M M E R window.
window.
53
simulation:
a. Concentration
Concentration and charge
charge for each ionic species of
for each of importance
importance
Diffusivity of
b. Diffusivity of ionic species
c. Forward
Forward and backward
backward reaction
reaction constant
constant values for
for each
each of
of reaction
reaction
d. T
Thermodynamic data for each
h e r m o d y n a m i c data each species
f. Angular velocity
Angular velocity of rotating disc electrode
of rotating electrode
g. W
Working
o r k i n g electrode potential with
electrode potential with respect
respect to SHE
SHE
Concentration of
Concentration of each ionic
ionic species is calculated
calculated from Visual Minteq
from Visual Minteq software.
software. Diffusivity
Diffusivity
electrolyte
electrolyte is calculated using electrochemical
calculated using electrochemical impedance
impedance spectroscopy. A
A default
default symmetry
symmetry
sensitivity
sensitivity analysis. Working electrode potential
W o r k i n g electrode potential with
with respect
respect to the standard
standard hydrogen
hydrogen
were conducted
were conducted using
using parallel
parallel plate electrodes. The rotating
rotating disc electrode
electrode equivalent
equivalent angular
The
T h e Sherwood
Sherwood nnumber for rotating
u m b e r for rotating disc electrodes
electrodes can be expressed shown in equation
expressed as shown equation
[3.36] [19-22].
0 5 0.33
o.ss 0 33
S h( rotating disc) = C R eroatating disc where C = 0.616 [3.36]
^h(rotating —
disc) C R e S c^
r o a t a t i n g d l s c
u J J
where C = 0.616
C [3.36]
54
[19-22].
S
S
==CRC R 0.33 S 0.33 (d e /
j ^ S r f / f
)0.33
3
[3.37]
[3.37]
hW
h p p .W c ~x
where d e = 2 x Channel
Channel height
e height height ~~ 1cm)
(channel height 1 cm)
x
X = flow
flow width
width (in parallel plate
plate electrode used
used in experiment
experiment spacing kept = 1cm)
spacing is kept cm)
C == 1.849 [20-22]
C [20-22]
4
Repp = Reynolds
=
Reynolds NNumber (for parallel
u m b e r (for parallel plate electrode) == 2.0
plate electrode) 2.0 xx 110
0 4
For water based solution Schmidt number can be assumed to be 1000 [12-15]
For water based solution Schmidt number can b e assumed to b e 1000 [12-15]
2
Reynolds nnumber = Re
umber = Rerotatingdisc = r wl
t ting disc =
ro a rotating disc)
fl (for rotating
w/u.
where r == radius of
where angular velocity; fl|i == kinematic
of disc; w == angular kinematic viscosity
Assumptions:
• Kinematic viscosity
Kinematic viscosity is assumed
assumed constant
• Reynolds number
n u m b e r for rotating disc electrode is a function
function of
of radius squared which can
can
By
B equating the Sherwood
y equating Sherwood nnumber
u m b e r for these cases, an equivalent
equivalent angular velocity of
angular velocity of rotating
electrode can
disc electrode can bbe written as equation
e written equation [3.38].
2
co- 1000XD[~]2
OJ= lOOOxZ) 1.86 x[Rx2]X2]O.66
x[R e
0M
[3.38]
[3.38]
r2 0.616
0.616 e
11 44
(0 = 10-
(D m2/s,
10"" m Rc = 2.0
/s, R 2
2.0 xx 10 , radius equivalent
e equivalent is calculated
calculated bby
y equating
equating area)
l.
1. Working
W o r k i n g electrode potential is entered
electrode potential entered in the input
input w
window
i n d o w (Figure 3.13). All other
2. By
B y clicking species information
clicking the species information icon, another window
another w i n d o w (Figure 3.14)
3.14) opens, where
where
By
3. B clicking the electrode
y clicking reaction window
electrode reaction w i n d o w another window
another w i n d o w (Figure 3.15)
3.15) appears
are entered.
Anodic
4. A and cathodic
n o d i c and cathodic reaction
reaction constants
constants are entered.
entered.
5. B
By clicking the experimental
y clicking experimental conditions
conditions icon another
another window
w i n d o w (Figure 3.16)
3.16) appears
appears
where information
where information related
related to angular
angular velocity
velocity and total solution
solution resistance
resistance are entered.
6. B
Byy clicking run icon
clicking the run icon output appear in
output will appear in the first w
window
i n d o w in the form
form of
of the total
Species
Species A
A Fe2+
jFe2+ 0.0847
100847 11 I-78870
1-78870 11 12 0.000000001
10.000000001
2
Species
Species 8B Fe3+
IFe3+ 1 0.00263)
0.0026~ 11 1-4600
•4600 11 13
(3 0.0000000008
10.0000000008
Species
Species C
C Fe
IFe 111 11 10. 11 r0o - - l 0.0000000001
0.o.o.o.o.o.o.o.o.o.1
Species
Species D
D H+
IH+ 0.235G32G21 11
10.235632621 10. 11 r1; - - 1 0.0000000093
0.o.o.o.o.o.o.o.o.93
Species
Species EE 102(aq) 0.00133
10.·00133 11 1116400
640.0 11 o
10 0.00000000226
10.0.0.0.0.0.0.0.0.226
Species
Species FF H20
H2O 111 11 1-237141
•237141 11 0 o - l 0.00000000224
r o.·o.o.o.o.o.o.o.o.224
Species G
Species G H2(aq)
IH2(aq) 0.000822
10.0.00.822 11 117600
17600 11 o
10 0.000000003
10.·0.0.0.0.0.0.0.0.3
Species
Species H
H OH-
10H- 0.000000000 11
10.0.00.0.0.0.0.00. 1-157328
-157328 11 1-1-1 0.00000000525
10.·0000.0.0.0.0525
·Species
Species I1 Cu
Icu 111 11 io
10. 11 0
ro---l 0.0000000001
o.·o.o.Oo.o.o.o.001
SpeciesJ
Species J Cu2+
ICu2+ 0.0078866
10.0078866 11 165520
J65520 11 12
2 0.000000000071
10.·0.0.0.0.0.0.0.0.0.0.71
Species K
Species K Zn2+
IZn2+ 111 11 11-147260
-147260. 11 ~ 10.·000.0.0.0.0.0.1
0.000000001
Species LL
Species Cu+
jCu+ 0.00000503
10.0.00.0.0.50.3 11 149980
499 80. 11 ~
1 00000000000053
10.000.0.0.0.0.0.00053
Species M
Species M SD42-
IS042- 111 11 1-744630.
|-744630 11 1-2
•2 0.000000001
10.·00.0.0.0.0.0.0.1
Species
Species N
N Na+
jNa+ 111 11 -261900
1-26190.0. 11 ~1 0.000000001
10.0.0.0.0.0.0.0.0.1
Species 00
Species CI-
CI- 10.348
0.348 11 1-131270.
i -131270 11 -1
1-1 10.00000000203
10. 0.0.0.0.0.0.0.0.20.3
Figure
F i g u r e 3.14: SIMMER
S I M M E R species ddata
a t a input.
input.
57
y | • ( § pel
Species
S p e c i e s IIdentities
denti1ies W
'IN C
0o 0
R U
*A: |Fe2*
jFe2+ B:
B: IFe3+
|Fe3+ C |Fe
C IFe D
D: IH+
j E: 1|02(aq)
02(aq) KKIl N
N
H +
N T
F: |H20
F: H: l:
I: jCu J: ICu2+ G E
IH20 G: IH2(aq)
G: |H2(aq) H: JOH-
10H- Icu J: |Cu2+ E R
L E
K: |Zn2t
fc
IZn2+ L: Izn
L: |Zn M: 1[s042-
M: 5042- N: JN
N: INa+ a+ 0: ICI-
[ci- E L
CC E
T
T C
c
R T
Electrochemical Reactions o0 R
DD 0
0
E D
D
Anod
Anod Cath
Cath
E E
E
Example Reaction: 1A + 2B
1A 2B + 2e- = 2C + D
D Alpha
Alpha Alpha
Alpha Rxn
R~n Rxn
R~n
Ca(h
Cath Anod
Anod Const
Const Const
, I1fB
1
n is" +
* Ir~ Ir * r
+r rr * r
r rr +
+ * F "rIA * +
-rrm +
11 e- = rlm+rr
m m fO"5 fD.5 fki8
J0.5 |05 |le18 10. 00~ p
|0.002i P r
F F *+
2 11fT
2
F Pro* r
f2 +r r * r r r
r *r m m
1 + I Im+ImIF+I" Ii+PIN
+ e- = N fO"5 f1:5 fk8
|0.5 |l.5 |le8 ~10 r rr
3 f4fD Fr;-i IEf * rr rr- rm rr +-f4- F f21F
+ + + F + 'mIr+rr
e- = r +r,r r<J0.5 f1.5
fO"5 jlj |000000 /4e24
< |4e24 rr 1000000 P
p
4 flIN + Ir rr- rr r r- rr rr +
+ + .r m mI Im+IF IT+rrt
e- = ' F+ f210
? fO"5
J0.5 |0.5 11200 fD.061
jD.5" f12OO" 10.001 p P r
~ flfT +Im I mr r rr rr f2^ - rll
+ + + m +rr
m +
e- mIr
= r + rr
r ID.5 jD.5" 10.072 ro.on
|0.5 |0.5 J0.072 p 10.072 P r
f1fL Ir r r* rr r r* rr rr f1* m1111m+Ir
EF T * +
E
+ + + m+
e- = 'mI +mIr [D.5 J0.5 \D.5
|0.5 res
|le8 res
|le8 9
p r
4
Figure
F i g u r e 3.15: SIMMER
S I M M E R eelectrochemical
l e c t r o c h e m i c a l rreaction
e a c t i o n input.
input.
58
58
P~i Experimental
Experimental Conditions
Conditions Data Entry
Entry Panel EGJ[Q)~
l ? !
Rotational Velocity
Rotational Velocity (RPM)
[RPM] 4S0
1480
Reference Electrode
Electrode
o
10
Potential (V)
Potential (V)
Boundary Layer
Layer Thickness
Thickness
(m) (defaults totointernal
(m) (defaults internal I
calculation iiff left blank)
blank)
Electrode Area
Electrode Area (m2)
(m2) |0.000426
10.000426
Ionic Strength
Strength (defaults
(defaults toto I
calculation ifif left
internal calculation left
blank)
Kinematic Viscosity
Viscosity (m2/sec)
(m2/sec)
(defaults to pure
pure water
watervalue value I
(0.000001) atat 40C
4oC ififleft
left
blank)
Estimated Uncompensated
Solution Resistance (Ohms)
(Ohms) 1|11
Resistance
Other Resistance |o
(Ohms) 10
Figure
F SIMMER
i g u r e 3.16: S I M M E R eexperimental
x p e r i m e n t a l cconditions
o n d i t i o n s iinput
n p u t window.
window.
59
Forward
Forward and backward
backward reaction
reaction constants
constants used
used in this simulation
simulation are determined
determined bby
y fitting
fitting
of these
value of these constants
constants are chosen
chosen close to the individual
individual reaction
reaction constant
constant for single
but for
reactions, but for complex mixed reaction
complex mixed reaction systems, the values
values were
were altered. SIMMER
SIMMER
simulation is then
simulation then performed
performed and adjustments
adjustments to kka and
and kb are m
a made
a d e until the difference
difference
between experimental
between experimental and
and simulated current efficiencies,
simulated current and experimental
efficiencies, and experimental and
and simulated
simulated
Based on reaction
3.2. Based reaction constant
constant values, current
current efficiency
efficiency is calculated. Total current
current (rate of
of
Figures 3.17
Figures 3.17 and
and 3.18
3.18 suggest assumed kka and
suggest that assumed and kb values
a values are better than higher
better than higher or
lower values
lower tested in
values tested in sensitivity
sensitivity analysis because
because they
they give
give the best
best fit with
with experimental
experimental
The
data. T current efficiency
h e current efficiency and current is also calculated
and total current calculated and
and shown Figures 3.17
shown in Figures 3.17 and
3.18
3.18 for one-tenth
one-tenth and
and tenfold
tenfold multiples
multiples of
of the best
best fitting
fitting k value to illustrate the sensitivity
sensitivity
of the response
of response variable
variable to changes
changes in kk value. Details of
Details of various parameters, diffusion
diffusion
Appendix A. The
Appendix The total rate of reaction and
of reaction and the rate of
of individual
individual electrochemical
electrochemical reactions
reactions
60
Table
T a b l e 3.2: Forward
F o r w a r d and
a n d bbackward
a c k w a r d cconstant
o n s t a n t vvalues,
a l u e s , eestimated
s t i m a t e d bby
y sensitivity
sensitivity analysis
analysis
Electrochemical
Electrochemical Reaction
Reaction kka a kkb b
(MoleL-'S-')
(MoleU'S" 1
(MoleL-1S-1)
(MoleL/'S" 1
18 0.002
Fee 3+ + e- -~ 2 1l xxl10
O 1 8
F 3 +
+ e- > Fe
Fe + 2 +
8 10
1 Xx 110
0 s
2H+ 2e" -~
2 H + 2e-
+
> H2
H 2
1 24
4e- -~ 4 xX l10
0 2 4
44H+
H + 0 2 + 4e"
+
> 2H
2 H2O0 2 2
1200 0.001
CuCb-
CuCl ~ + ee-~~
2 ^ CCu
u + 2CI
2Cl
0.072 0.072
Cuu 2+++2e-
C 2 +
2e' ~ Cuu
-^C
8 8
1l xX l10
O 8
1l xX l10
O 8
Cu+
Cu + e" -~
+e- > Cu
+
80
70 r
o Expt
r- • kl10
>.
(J
60 ~
ok
c
010 k
'u 50
<II r-
I- r-
f<II 40
-c
...~::J 30
r-
r
() 20
0
10
0 -
Cu01- Cu09- Cu01-
Cu01- Cu09- Cu01-
Cu01- Cu09- Cu01- Cu09-
09Fe01- 01Fe01-
01Fe01- 09Fe09- 01Fe09- 09Fe01- 01Fe01-
09Fe01- 01Fe01- 09Fe09- 01Fe09-
09H05 09H05 01H05 01H05 09H15 09H15 01H15 01H15
10
Test ID
Figure
F i g u r e 3.17: E
Experimental
x p e r i m e n t a l and
a n d ttheoretical
h e o r e t i c a l current efficiency aand
c u r r e n t efficiency sensitivity analysis
n d sensitivity analysis for
for
different Ka values.
different K v a lau e s .
61
9
8 o Expt . k r-
r-
7 o kl10 010 k r-
~ 6 -
-c::
~ 4
5
I:
r-
r-
f0-
r-
r-
-
-
r-
r-
<3 3
2
r,
1
o .....
Cu01 -
Cu01- Cu09-
Cu09- Cu01-
Cu01- Cu09-
Cu09- Cu01-
Cu01- Cu09-
Cu09- Cu01-
Cu01- Cu09-
Cu09-
09Fe01-
09Fe01- 01Fe01-
01Fe01- 09Fe09-
09Fe09- 01Fe09-
01Fe09- 09Fe01-
09Fe01- 01Fe01-
01Fe01- 09Fe09-
09Fe09- 01Fe09-
01Fe09-
09H05
09H05 09H05
09H05 01H05
01H05 01H05
01H05 09H15
09H15 09H15
09H15 01H15
01H15 01H15
01H15
Test ID
Test 10
Figure
F i g u r e 3.18: Experimental
E x p e r i m e n t a l aand
n d ttheoretical
h e o r e t i c a l ccurrent
u r r e n t density
d e n s i t y and sensitivity aanalysis
a n d sensitivity n a l y s i s for
for
different K
different Ka values.
values.
a
62
are outputs
outputs of
of SIMMER.
S I M M E R . An
A n E vs. log (I) graph can
(1) graph can also bbee plotted
plotted for
for all simulations
simulations using
SIMMER
S I M M E R data.
simulated current
simulated current and
and potential
potential relationship
relationship match
match reasonably
reasonably well with
with experimental
experimental
potentiodynamic results.
potentiodynamic
3.4.2 Analysis of
3.4.2 Analysis of Electroplated
Electroplated sample
sample
Characterizations of
Characterizations of electrodeposited
electrodeposited samples were performed
samples were performed bby image analysis. One
y image O n e of
of
surface coverage
the analyses is surface of electrodeposited
coverage of copper for
electrodeposited copper for various
various test
test conditions.
Images of
of various samples were evaluated using Image
evaluated using software. B
Image J software. By using proper
y using proper threshold
threshold
adjustment conditions
adjustment conditions a color
color image
image can
can bbe changed into a black
e changed black and white
white format
format and
and the
percentage of
percentage of coverage
coverage of black and white
of black white pixels
pixels can
can bbee calculated.
calculated. Hence
Hence in this way
way
percentage of surface
percentage coverage of can bbee calculated.
surface can calculated.
_ _ of electrode
total area of electrode covered
covered by
by electrodeposit
electrodeposit .„
P
Percentage coverage == ----------------''---------''----
ercentage 0orf coverage [3.40]
[3.40J
total area of electrode
total area of electrode
Percent coverage
Percent of various
coverage of various electrodeposited
electrodeposited samples compared and shown
samples are compared shown in Figure
3.21. Percent
Percent coverage
coverage is also compared with current
compared with current efficiency
efficiency in Figure
Figure 3.22. It can
can be
be
0.4
0.2
-0.4
b&
log(l)
Figure
F i g u r e 3.19: Experimental
E x p e r i m e n t a l and
a n d simulated
s i m u l a t e d current
c u r r e n t and
a n d potential
p o t e n t i a l rrelationship
e l a t i o n s h i p for test id
for test id
CuOl-09FeOl-09HOS.
C u 0 1 - 0 9 F e 0 1 - 0 9 H 0 5 . Details
Details of of experiments
e x p e r i m e n t s are
a r e listed
listed in Table
T a b l e 2.2.
-6*
By SIMMER
-+-By
_ Experimental 0.5
0.3
CL
s-ur>
LU -3.5
-3.5
-0 .3
-0.3
-0.5
10g(l)
log(i)
Figure
F i g u r e 3.20: Experimental
E x p e r i m e n t a l and
a n d simulated
s i m u l a t e d current
c u r r e n t and
a n d ppotential
o t e n t i a l rrelationship
e l a t i o n s h i p for
for test id
CuOl-09Fe09-01H1S. Details of
C u 0 1 - 0 9 F e 0 9 - 0 1 H 1 5 . Details of experiments
e x p e r i m e n t s are
a r e listed
listed in Table
T a b l e 2.2.
64
100
80
;e-
o
Q) 60
C)
...IV
~ 40
o
u
20
o
Cu01- Cu09- Cu01- Cu09- Cu01- Cu09- Cu01- Cu09-
09Fe01- 01Fe01- 09Fe09- 01Fe09- 09Fe01- 01Fe01- 09Fe09- 01Fe09-
09H05 09H05 01H05 01H05 09H15 09H15 01H15 01H15
T e s t 10
Test ID
Figure
F i g u r e 33.21:
. 2 1 : Comparison of ppercentage
C o m p a r i s o n of e r c e n t a g e coverage.
coverage.
60
50 • [[ ]]
~
c 40
CD
'u
•
In 30 A
C +
+ •• Cu01-09Fe01- 09H05
Cu01-09Fe01-09H05
~ •• Cu09-01
Cu09-01Fe01- 09H05
Fe01-09H05
x
X
::::I 20 D.. Cu01-09Fe09-01
ACu01-09Fe09- H05
01H05
0 Cu09-0 1 Fe09-01
Cu09-01Fe09- H05
01H05
•o Cu01-09Fe01- 09H15
Cu01-09Fe01-09H15
10 • Cu09-01
Cu09-01Fe01 09H15
Fe01-09H 15
+ Cu01-09Fe09- 01H15
+ Cu01-09Fe09-01 H 15
-Cu09-01 01H15
Fe09-01
-Cu09-01Fe09- H15
0
00 220
0 440
0 60
60 880
0 100
100
Percent
P e r c e n t coverage
coverage
Figure
F i g u r e 3.22: C
Comparison
o m p a r i s o n of
of ppercentage
e r c e n t a g e ccoverage
o v e r a g e and
a n d efficiency.
efficiency.
65
It is observed
observed that
that m
minimum coverage is for high
i n i m u m coverage high cupric
cupric and high
high ferric ion
ion concentration.
concentration.
maximum
In contrast, m a x i m u m coverage observed for the low
coverage is observed low cupric and low ferric ion
as expected.
expected.
A factorial
A factorial design matrix
matrix was designed
designed in order measure effects
order to measure effects of
of three variables (A, B
and C) on
and on the desired
desired process
process output
output variable. Eight
Eight experiments required for
experiments are required for a 3-factor,
3-factor,
2-level
2-level design. A represents the ratio of
A represents cuprous ion, B
of cupric and cuprous B represents
represents the ratio of
of
ferric and
and ferrous ion
ion and C
C represents
represents the HC1
HCI concentration. As
As A, Band
B and C are presumed
presumed to
determine
determine the effect
effect of change in
of change in level of
of the variable
variable on the output. In Table
Table 3.3, the high
for interactions
interactions A
A with
with B
B,, A
A with
with C, B with C and
B with and A
A with
with B
Band C are represented
and C represented bby
y AB,
AB,
AC,
A BC
C, B and A
C and ABC,
B C , respectively. The relative effects of such interactions
effects of interactions on the observed
observed
From
From the results of factorial design
of the factorial design analysis, it can bbee concluded
concluded that high
high ferric to
can bbe
e observed visually in Figures
observed visually Figures 3.23 and 3.24. Figure 3.23 shows
shows that
that electrodeposition
electrodeposition
3 2
as well as surface coverage is reduced
surface coverage reduced for
for electrolytes with high
electrolytes with high (Fe +/Fe
/Fe +). High content
). High content of
of
acid
acid as well as high
high cupric/cuprous
cupric/cuprous ratio also causes an adverse effect
effect on
electrodeposition/current efficiency.
electrodeposition/current efficiency.
66
T a b l e 33.3:
Table Factorial
.3: F a c t o r i a l ddesign matrix
esign m a t r i x ooutput for experiments,
u t p u t for e x p e r i m e n t s , ddiscussed in section
i s c u s s e d in section 2.4.3.
2 /Cu+ Fee3+lFe 2
Run Cu
Cu +/Cu
2+ +
F 3
W + +
HCI
HC1 Current
Current Observed
Observed
Test ID
Test A B C Efficiency
Efficiency Value
(%)
(%)
CuOl-09FeOl-09H05
Cu01-09Fe01-09H05 1 - - - 54 Yll
Y
Cu09-01FeOl-09H05
Cu09-01Fe01-09H05 2 +
+ - - 51.6 Y2
Y 2
CuOl-09FeOl-09HI5
Cu01-09Fe01-09H15 5 - - +
+ 47 Y5
Y 5
Cu09-0 1F eO 1-09H 15
Cu09-01Fe01-09H15 6 +
+ - +
+ 40 Y6
Y 6
CuOl -09Fe09-01HI5
Cu01-09Fe09-01H15 7 - +
+ +
+ 27 Y7
Y 7
Cu09-0 1F e09-0 1H 15
Cu09-01Fe09-01H15 8 +
+ +
+ +
+ 28 Y8
Y 8
Effects of
Effects different variables
of different variables and interaction
interaction parameters
parameters are:
2
( A )=
(A) - ((Cu
C u +/Cu+)
2+
=--4.6
/Cu ) = +
4.6 (effect
(effect of variable A)
of variable
2
(B) = ((Fe3+/Fe
F e 3 / F e +)
+
) = -20.9
2+
(effect
(effect of variable B)
of variable
(HCl) = -4.4
(C) = (HC1) (effect of variable
(effect of variable C)
(AB) == 0.1
(AB) 0.1 (interaction parameter)
(interaction parameter)
(AC) ==11.6
(AC) .6 (interaction parameter)
(interaction parameter)
(BC) == 4.9
(BC) (interaction parameter)
(interaction parameter)
(ABC) == 3.9
(ABC) 3.9 (interaction
(interaction parameter)
parameter)
Mean
M e a n = 37.7
67
Figure
F i g u r e 3.23: Images of electroplated
I m a g e s of e l e c t r o p l a t e d ssamples, test cconditions
a m p l e s , test o n d i t i o n s are e p r e s e n t e d in
a r e rrepresented in Table
Table
2.2.
68
>
Test
Test ID CuOl-09PeOl-09H15
Cu01-09Fe01-09H15 Test ID Cu09-01PeOl-09H15
Test Cu09-01Fe01-09H15
—•
Test
Test ID CuOl-09Pe09-01H15
Cu01-09Fe09-01H15 Test
Test ID Cu09-01Pe09-01H15
Cu09-01Fe09-01H15
Figure
F i g u r e 3.24: IImages of eelectroplated
m a g e s of l e c t r o p l a t e d samples, test conditions
s a m p l e s , test c o n d i t i o n s aare
r e rrepresented
e p r e s e n t e d in
in Table
Table
2.2.
69
This trend
trend can bbe represented in Figure
e represented Figure 3.25, where
where it can bbee observed
observed that
that high
high current
already been
been reported
reported that
that electrolysis
electrolysis of
of cupric chloride
chloride causes corrosion
corrosion of
of copper
copper cathode
explanation reduction of
explanation for the reduction current efficiency
of current dissolution of
efficiency is the dissolution of copper
copper cathode
cathode in
presence of
presence of cupric ions [13]. Current
Current efficiency
efficiency drops with
with increasing
increasing concentration of ferric
concentration of ferric
evident from
ions as is evident factorial design
from factorial design experiments well as simulation.
experiments as well Power
reduction potential
reduction potential for Fe / F e21 is 0.77
F e 3+/Fe
3 + 2 +
0.77 V
V and
and that Cuu 2+ /Cu
that for C 2 +
/Cu is 0.34V. Thus, w
when
h e n ferric
ferric
present during
ion is present during electrowinning, reduction of ferric ion
reduction of ion takes place
place first which consumes
first which consumes
m u c h of
much These ions reduce
of the current. These reduce rapidly
rapidly as they
they diffuse
diffuse to the surface. High
dissolution of
dissolution of cathode
cathode due to chloride ion presence
presence has also been
been reported
reported [13]. Hydrochloric
Hydrochloric
acid
acid is a source
source of
of chloride
chloride ions, and
and it therefore
therefore has an adverse effect
effect on electrowinning
on electro winning
current efficiency.
current efficiency.
3.5 Analysis
Analysis of
of electro winning test matrix
electrowinning matrix II
Output
Output of matrix II (Table 2.4) confirms
of test matrix of factorial
confirms the results of factorial design
design experiments
experiments as
When
W h e n the relative concentration of
relative concentration of ferrous ion
ion increases, current efficiency also increases. On
current efficiency On
Figure 3.26
Figure 3.26 represents current efficiency for
current efficiency for each
each experiment.
experiment.
70
21>1>(3_0)
2**(3-0) design
design
. >70
. <70
. <60
D <50
0<40
. <30
. <20
'0
70
~ 60
"
>.
(.) 50
r:::
.~
40
--
(.)
;;:::
w 30
r:::
......
<II 20
::J
u 10
0
Test 10
Figure
F i g u r e 3.26: C Current
u r r e n t efficiency
efficiency is pplotted for each
l o t t e d for Test
each T e s t IID
D bbased on tests
a s e d on tests aand
n d condition
condition
in
in Table
T a b l e 22.3.
.3.
shows current
current efficiency
efficiency decreases as a function
function of
of increasing
increasing ferric ion
ion concentration.
concentration.
According to results of
According of factorial design experiments
factorial design high cupric/cuprous
experiments high cupric/cuprous ratio also causes an
adverse effect
adverse effect on
on electro- deposition/current
deposition/current efficiency.
efficiency. This is evident from Figure 3.28,
evident from
which shows
which shows an increase
increase in concentration of cupric ion
concentration of that is associated
ion that associated with
with the reduction
in current
current efficiency.
efficiency.
72
60
50
~
~
~ 40
r::
CI)
'ij
IE 30
...r::
w
20
......
CI)
0 I 1 1 1 1 1 1
0
0 0.02
0.02 0.04
0.04 0.06
0.06 0.08
0.08 0.1
0.1 0.12
0.12
Concentration of
Concentration of Ferric
Ferric Ion
Ion (mole/I)
(mole/I)
Figure
F i g u r e 3.27: Current efficiency is pplotted
C u r r e n t efficiency for different
l o t t e d for different fferric ion concentration.
e r r i c ion concentration.
60
50
>-
(.)
c: 40
,~
--
(.)
;;:::
CI)
c:
....
CI)
30
....
::J 20
U
10
0 > 1 1 1
Very low
Very low Very
Veryhigh
high
Cuprous ion to cupric ion ratio
Figure
F i g u r e 3.28: Current
C u r r e n t efficiency
efficiency is ccompared for cuprous
o m p a r e d for ion to ccupric
c u p r o u s ion ion ratio
u p r i c ion ratio
(low for
(low test IID
for test CulO-OOFeOO-OO aand
D CulO-OOFeOO-00 n d hhigh
i g h for test IID
for test D CuOO-lOFeOO-OO).
Cu00-10Fe00-00).
CHAPTER
C HAPTER 4
CONCLUSIONS
C ONCLUSIONS
3 2 2
Reasonable infonnation
Reasonable regarding the effects
information regarding of Fe
effects of Fe +,, Fe + , Cu
Cu +,, Cu
Cu+ and hydrochloric
hydrochloric
acid concentration
concentration on chalcopyrite leaching as well as electrowinning
chalcopyrite ore leaching electrowinning of
of copper
copper using
chloride media
chloride media has been
been detennined modeled in this study. Integration
determined and modeled Integration of
of leaching
leaching
chalcopyrite
chalcopyrite ore and
and electrowinning of copper
electrowinning of copper was carried out
out using
using calcium
calcium chloride
chloride and
electrowinning, may
electrowinning, m a y be possible.
feasible at hydrochloric
feasible hydrochloric acid and
and cupric ion concentrations of 0.15 mole/1
concentrations of molell and 0.09
0.09 mole/l
mole/1
respectively. Factorial
Factorial design experiments
experiments analysis showed weak signs of
showed weak of a small negative
effect of
effect of ferric/ferrous
ferric/ferrous ion ratio on
on recovery.
Electrowinning of
Electrowinning of copper
copper from chalcopyrite ore using
from chalcopyrite using chloride m
media
e d i a was shown
shown to be
be
possible at low
possible low acid (0.05 mole/1)
molell) concentration
concentration and low cupric ion (0.01 mole/I)
mole/1)
concentration. High
High ferric ion
ion concentration
concentration has the m
maXImum adverse effect
a x i m u m adverse effect on
deposition quality) in
deposition in short
short tests was measured
measured and
and found
found to bbe consistent with
e consistent with expected
expected
Current efficiency
Current efficiency values
values simulated
simulated using
using SIMMER software showed
S I M M E R software good agreement
showed good agreement
potentiodynamic scans w
potentiodynamic were in good
e r e in good agreement with measured
agreement with measured data.
APPENDIX
A PPENDIX A
A
IIMAGES
M A G E S OF
O F ELECTROPLATED
E L E C T R O P L A T E D SAMPLES
SAMPLES
76
FIgure A
Figure AI:
l : Image of
electroplated
electroplated sample (Test Figure A2: Image of
of Figure A3: Image ofof
Id: CulO-OOFeOO-OO),
Id: Cul0-00Fe00-00), electroplated
electroplated sample electroplated sample (Test
electroplated
details of
of experiment
experiment are (Test Id: CuOO- Id: CuOO-IOFeIO-OO),
Cu00-10Fel0-00),
given in Table 2.4. IOFeOO-OO), details of
10Fe00-00), of details of experiment are
of experiment
experiment
experiment are given given in Table 2.4.
in Table 2.4.
A4 : Image of
Figure A4: of
electroplated
electroplated sample (Test
Id: CuOI-09Fe05 -05),
Cu01-09Fe05-05),
of experiment
details of experiment are
given in Table 2.4.
Figure AAll:
l l : Image of
of Figure A12: Image of
of Figure A13: Image ofof
electroplated sample (Test
electroplated electroplated sample (Test Id:
electroplated electroplated
electroplated sample (Test
Id: Cu03-06Fe05-05), Cu02-08Fe05-05), details of
Cu02-08Fe05-05), Id: CuO
Id: I-09Fe05-05),
Cu01-09Fe05-05),
details of experiment are
of experiment experiment
experiment are given in Table of experiment
details of experiment are
given in Table 2.4. 2.4. given in Table 2.4.
APPENDIXB
A PPENDIX B
CONCENTRATION
C OF
ONCENTRATION O IONIC SPECIES
F IONIC SPECIES
79
0.09
0. 0 9
0.08
0. 0 8 - •oCCu01-09Fe01
u01-09Fe01-09H05
-09H05
•• Cu09-01 Fe01-09H05
Cu09-01Fe01 -09H05
.... 0.07
£~ 0. 0 7 o
• Cu01-09Fe09-01
Cu01-09Fe09-01H05H05
i
11:: o
• Cu09-01 F e09-01 H05
Cu09-01Fe09-01H05
06
1 0o..06 .• Cu01-09Fe01-09H15
Cu01-09Fe01 -09H15
Cu09-01Fe01
•1:1 Cu09-01 -09H15
Fe01-09H15
~
f 0 o..05
05 •• Cu01-09F
Cu01-09Fe09-01H15
e09-01 H15
Ii.... „ o
• Cu09-01 Fe09-01 H15
Cu09-01Fe09-01H15
::s 0.
0. 04
04
4)
1~ 0.03
;:; 0 03
u
u
0.02
0. 02 -
0.0
011
o0 ['1 an j
1L - ruin , nj~i I I I i
CuCI (01<1)
CuCl (a<|) CuCI+
C11CI+ CuCI?-
CuCI2- CuCI?
CuCI2 CuCI3-
CuCI3- CuC13-2 CuCI4-?
CuCI3-2 CuCI4-2 CuOH+
C11OH+
(01<1)
(aq)
Figure
Figure B Bl:
l : Concentration
C o n c e n t r a t i o n of
of different
different ccopper
o p p e r ccomplexes in solution
o m p l e x e s in solution ((determined
d e t e r m i n e d using
using
Visual
V i s u a l Minteq software) for
M i n t e q software) for different
different test
test IIDs, details of
D s , details of experiments
e x p e r i m e n t s are listed in
a r e listed in Table
Table
2.2.
0 .000025 -,
0.000025
^ 0.00002
0.00002 •C Cu01-09Fe01-09HOS
Cu01-09Fe01-09H05
-
-;-
I
...0)
u
*i
::::CIJ
'0 0 .000015
•• CU09-01
o
o
Cu09-01Fe01-09H05
Fe01-09HOS
Cu01-09Fe09-01
• CU09-01
HOS
• Cu01-09Fe09-01H05
Fe09-01 HOS
Cu09-01Fe09-01H05
I 0.000015
E
'E'
~c • Cu01-09Fe01-09H15
Cu01-09Fe01-09H1S
.2
0
*•>
;; •C Cu09-01Fe01-09H15
CU09-01 Fe01-09H15
-...nI
s::::
ICIJ
0
s::::
0.00001
0.00001
•
•o
Cu01-09Fe09-01H15
Cu01 -09Fe09-01 H15
Cu09-01 Fe09-01 H15
Cu09-01Fe09-01H15
0
Uo 0 .000005
0
0.000005
0
Cu+1
Cu+1
Figure B2:
Figure B Concentration
2: C of cuprous
o n c e n t r a t i o n of c u p r o u s ions inin solution
s o l u t i o n ((determined
d e t e r m i n e d uusing
sing V Visual
i s u a l Minteq
Minteq
software) for different
software) for different test test IIDs, details of
D s , details of experiments
e x p e r i m e n t s are listed in
a r e listed in TTable
a b l e 2.2.
80
80
0 .08
0 .07
Q)
• Cu01-09Fe01-09H05
Cu01 09Fe01-09H05
~
... 0.06 •• CU09-01 Fe01 -09H05
Cu09 01Fe01-09H05
::::::
Q) o• Cu01-09Fe09-01 H05
Cu01 09Fe09-01H05
'0 0 .05 o• CU09-01 Fe09-01 H05
Cu09 01Fe09-01H05
E
C •• Cu01-09Fe01-09H15
CuOt 09Fe01-09H15
0 0.04
:;::; o• Cu09-01Fe01-09H15
Cu09-01Fe01-09H15
-...
co
s::: 0 .03
Q)
()
s:::
•• Cu01-09Fe09-01
Cu01-09Fe09-01H15
o• CU09-01
H15
Cu09 01Fe09-01H15
Fe09-01 H15
0 0.02
()
0 .01
Cu+2
Cu+2
Figure
F i g u r e B3:
B 3 : Concentration
C o n c e n t r a t i o n of
of cupric
c u p r i c ions in solution
solution (determined
( d e t e r m i n e d using
u s i n g Visual
V i s u a l Minteq
Minteq
software)
software) for for different
different test IDs, I D s , details of of experiments
e x p e r i m e n t s are
a r e listed in TableT a b l e 2.2.
0.09
0 .09 i
0.08
-:-:::...
-sr
Q) o.07
0.07
o• Cu01-09Fe01
• Cu09-01
-09H05
Cu01-09Fe01-09H05
Fe01-09H05
Cu09-01Fe01-09H05
aQ) 00.06
.06 •o Cu01-09Fe09-01 H05
Cu01-09Fe09-01H05
'0 o Cu09-01 Fe09-01
• Cu09-01Fe09-01H05 H05
SE 00.05
C .05 • Cu01-09Fe01-09H15
Cu01-09Fe01-09H15
0
:;::;
0.04 •o Cu09-01 Fe01-09H15
Cu09-01Fe01-09H15
-...co 0 .04
s::: • Cu01-09Fe09-01
Cu01-09Fe09-01H15
H15
o()
Q) 0.03 o CU09-01 Fe09-01
• Cu09-01Fe09-01H15 H15
s:::
0
O 0.02
() 0 .02
0.01
0.Q1
CuCI2-
C uCI2- CuCI2
C u C I 2 (aq)
(aq)
FFigure
igure B B4: Concentration
4: C of different
o n c e n t r a t i o n of different cchloro
h l o r o ccomplex of ccopper
o m p l e x of in solution
o p p e r in solution (determined
(determined
uusing
sing V Visual
isual MMinteq software) for
i n t e q software) for different
different testtest IIDs, details of
D s , details of eexperiments
x p e r i m e n t s aare listed in
r e listed in
TTable
a b l e 2.2.
81
81
0 .000035
0.000035
0.00003
--:e
CIl
j~ 0.000025
•C
•
Cu01
Cu01-09Fe01-09H05
09Fe01- 09H05
CU09-0 1Fe01-09H05
Cu09 01Fe01- 09H05
CIl •o Cu01-09Fe09-01 H05
Cu01 09Fe09-01H05
"5
'0 •o CU09-01 Fe09-01
Cu09 01Fe09- H05
01H05
E 0 .00002
£ 0.00002
~
;0
•
C•
Cu01 09Fe01- 09H15
Cu01-09Fe01-09H15
CU09-01 Fe01-09H15
Cu09 01Fe01- 09H15
...
III 0.000015
1:2 0.000015 • Cu01 09Fe09-01H15
Cu01-09Fe09-01 H15
CIl •o Cu09-01Fe09-01H15
Cu09-01Fe09 -01H15
§ 0 .00001
0.00001
(,)
0.000005
0.000005
CuCI3-
CuCI3-
Figure
F B5:
igure B 5: CConcentration of C
o n c e n t r a t i o n of CuCh-
u C ^ " in solution
solution ((determined
d e t e r m i n e d uusing
sing V Visual
i s u a l Minteq
Minteq
software) for different
software) for different test test IIDs, details of
D s , details of eexperiments
x p e r i m e n t s are listed in Table
a r e listed T a b l e 2.2.
0.00000008
0.00000008
0.00000007
0 .00000007
Q) • Cu01-09Fe01-09H05
Cu01-09Fe01-09H05
... 0.00000006
?jg
:t:
0.00000006 • Cu09-01Fe01-09H05
Cu09-01Fe01-09H05
~
CIl •o Cu01-09Fe09-01H05
Cu01-09Fe09-01H05
"5
(5 00.00000005
.00000005
•o CU09-01 Fe09-01 H05
Cu09-01Fe09-01H05
E
E,
Co0 00.00000004
.00000004 1
• Cu01-09Fe01-09H15
Cu01-09Fe01-09H15
; Oc CU09-01 Fe01-09H15
Cu09-01Fe01-09H15
...2
III
Cu01-09Fe09-01H15
• Cu01-09Fe09-01H15
1: 0.00000003
0 .00000003
CIl o
• Cu09-01 Fe09-01 H15
Cu09-01Fe09-01H15
(,)
oc::
o0 00.00000002
(,)
.00000002
o
0 .00000001
0.00000001
0
0
CuC14-2
CuCI4-2
0.1
0.1
0.09
-...
_
~
a
Q)
0.08
0.08 •
••
Cu01-09Fe01-09H05
Cu01-09Fe01 -09H05
Cu09-01Fe01-09H05
CU09-01 Fe01-09H05
| 0.07
0.07
Q;o o• Cu01-09Fe09-01H05
Cu01-09Fe09-01 H05
"0 0.06 o• Cu09-01Fe09-01H05
CU09-01 Fe09-01 H05
E| 0.06
l: •• Cu01-09Fe01-09H15
Cu01-09Fe01-09H15
0
§ 0.05
0.05
:;:; o• Cu09-01Fe01-09H15
Cu09-01Fe01-09H15
......
ctS
(0
I:
4=
0.04
0.04
• Cu01-09Fe09-01H15
CUO 1-09Fe09-0 1H15
Q)
•
o Cu09-01Fe09-01H15
CU09-01 Fe09-01 H15
CJ
c
I:
0.03
0o
uo 0.02
0.03 -I
o
0.01
° 0.02
0
0.01
Fe+2
Fe+2
0
Figure
F B7:
igure B C o n c e n t r a t i o n of
7 : Concentration of fferrous solution (determined
e r r o u s ions in solution ( d e t e r m i n e d uusing
sing V Visual
i s u a l Minteq
Minteq
software) for different
software) for different test test IDs. details of
I D s . details of eXDeriments
e x o e r i m e n t s aare listed in T
r e listed Table
a b l e 2.2.
0.035
0.03
-...
~
Q)
::::::
0.025
Cu01-09Fe01-09H05
HCu01-09Fe01-09H05
• Cu09-01Fe01-09H05
Cu09-01Fe01-09H05
Q) •o Cu01-09Fe09-0 1H05
Cu01-09Fe09-01H05
"0 o CU09-01 Fe09-01
• Cu09-01Fe09-01H05H05
E 0.02
l: • Cu01-09Fe01-09H15
0
:;:; OCu09-01Fe01-09H15
o Cu09-01Fe01-09H15
......
ctS
I:
0.015
• Cu01-09Fe09-01H15
Q)
CJ •o CU09-01
Cu09-01Fe09-01H15
Fe09-01 H15
I: 0.01
0
u
0.005
Fe+3
F e+3
Figure
F B8:
igure B Concentration
8: C of fferric
o n c e n t r a t i o n of ions in
e r r i c ions in solution
solution ((determined
d e t e r m i n e d uusing
sing V Visual
i s u a l Minteq
Minteq
software) for
software) for different
different test test IIDs, details of
D s , details of eexperiments
x p e r i m e n t s aare listed in
r e listed in TTable
a b l e 2.2.
83
1.6E-09 ^
1.4E-09 -
C Cu01-09Fe01 -09H05
HCu01-09Fe01-09H05
lit re)
...
Q)
1.2E-09 •• Cu09-01Fe01-09H05
Cu09-01Fe01-09H05
:!:
Q;
"a> o• Cu01 -09Fe09-01 H05
Cu01-09Fe09-01H05
'0o 11E-09
E-09 o• Cu09-01 Fe09-01 H05
Cu09-01Fe09-01H05
E
I: •• Cu01-09Fe01-09H15
Cu01-09Fe01-09H15
nti at ion
0 8E-10 -
:;; o0CuO9-O1FeO1-O9H15
Cu09-01 Fe01-09H15
-...
C'a
r:::::
Q)
0C
O
D
6E-10 •• Cu01
Cu01-09Fe09-01H15
-09Fe09-01 H15
o• Cu09-01
Cu09-01Fe09-01H15
Fe09-01 H15
c0
r:::::
4E-10 -
uOo
2E-10
0 -
FeOH+
FeOH+
Figure
F i g u r e B9:
B 9 : Concentration
C o n c e n t r a t i o n of
of FeOH+
F e O H ions in solution
+
solution (determined
( d e t e r m i n e d using
using V Visual
i s u a l Minteq
Minteq
software)
software) for different
different test D s , details of
test IIDs, of experiments
e x p e r i m e n t s are
a r e listed in TableT a b l e 2.2.
0.003
0 .003
0.0025 -
-. Cu01 -09Fe01
• Cu01- 09Fe01--09H05
09H05
...
:t:
Q)
•• Cu09-
Cu09-01Fe01
01Fe01--09H05
09H05
=:::: [] Cu01 -09Fe09-01 H05
Q) 0 .002 • Cu01- 09Fe09- 01H05
'0 [] CU09-01
• Cu09- Fe09-01 H05
E 01Fe09- 01H05
C 0 .0015
• Cu01-
Cu01 -09Fe01
09Fe01--09H15
09H15
0
:;; [J Cu09-01Fe01-09H15
m Cu09-01Fe01- 09H15
...C'a • Cu01-
Cu01-09Fe09-01H15
09Fe09-01H15
1:
Q) 0 .001 []
• Cu09-01Fe09-01H15
Cu09-01Fe09 -01H15
g
0
U
0.0005
FeOH+2
F eOH+2
2
FFigure BIO:
igure B 10: CConcentration of FFeOH
o n c e n t r a t i o n of e O H + ions
ions inin solution
solution ((determined
d e t e r m i n e d uusing
sing V Visual
i s u a l Minteq
Minteq
software) for
software) for different
different test test IIDs, details of
D s , details of eexperiments
x p e r i m e n t s aare listed in TTable
r e listed a b l e 2.2.
APPENDIXC
A PPENDIX C
EXPERIMENTAL AND
EXPERIMENTAL A N D SIMULATED CURRENT
SIMULATED C DENSITY
URRENT D E N S I T Y AND
AND
CURRENT POTENTIAL
CURRENT P O T E N T I A L RELATIONSHIP
RELATIONSHIP
FOR
F O R DIFFERENT
D I F F E R E N T TESTS
TESTS
85
• BySIMMER
-+-By SIMMER 0.6
—•-By SIMMER
-+-By SIMMER
0.5
___ Experimental
•Experimental _ _ Experimental 0.5
0.4
• Experimental
0.3
0.3
0.2
-*.55 -4 -3 .5
-3.5 -3 -2.5 * -3.5
-3.5 -3
-3
-0.6
-0.5
-0.5 -
fc*-
10g(l)
log(i)
Figure C
Figure C1:
I : Potential
Potential Vs log |i| Iii Figure C2: Potential
Figure Vs log |i|
Potential Vs Ii i
graph
graph for Test Test Id Cu09-0
C u 0 9 - 0 11F eeO0 11-- graph forfor Test
Test Id Cu01-09Fe09-
009H05, of experiment
9 H 0 5 , details of experiment are 001H05,
1 H 0 5 , details of
of experiment
experiment are
given in Table
given Table 2.3. given
given in Table
Table 2.3.
-6T6-
~BySIMMER• By SIMMER -+-By
• BySIMMER
SIMMER
0.6 0.4
_ ___ Experimental 0.4
•Experimental
Experimental • Experimental
0.4
0.2
0.2
0.2
-3.5 -3 -A5
5
-0.4
-0.6
109(1)
log(l)
Figure C
Figure C3:3 : Potential
Potential Vs log log |i|
Iii Figure C4: Potential
Potential Vs Vs log |i|
Ii i
graph
graph for Test Test Id Cu09-
Cu09- graph for Test Test Id CuOCuOl-1-
1 F e 0 9 - 0 1 H 0 5 , details of
001Fe09-01H05, of 09Fe01-09H05,
0 9 F e 0 1 - 0 9 H 0 5 , details of
of
experiment
experiment are given in Table
Table experiment
experiment are given Table
given in Table
2.3. 2.3.
86
__ By SIMMER -+-By
• BySIMMER
SIMMER
• By SIMMER 0.4 _ _ Experimental 0.5
0.5
___ Experimental
• Experimental • Experimental
0.2
0.3
0.3 H
~ Q
w ~
5 -4 -3.5 w
-4.5 •1 -3.5
-3.5 -3
-0.3
-0.3
-0.4
-0.5
-0.5
10g(l)
log(l)
10g(l)
log(i)
Figure C5:
Figure Potential Vs
C 5 : Potential Vs log |i|
Iii Figure C6: Potential
Potential Vs log |i| Iii
graph for Test
graph Test Id Cu09-01FeOl-
Cu09-01Fe01- graph for Test Test Id CuOCuOl-1-
009H
9 H 115,
5 , details of experiment are
of experiment 09Fe09-01HI5,
0 9 F e 0 9 - 0 1 H 1 5 , details of
of
given in Table
given Table 2.3. experiment
experiment are given given in Table
Table
2.3.
-Mr
__ By SIMMER
—•-By SIMMER
-+-By SIMMER • By SIMMER
0.5 ___ Experimental 0.4
0.4
_•_ Experimental
Ex perimental 0.5 • Experimental
0.3
0.3 0.2
0.2
;- ~
w
w •X ~-3.5
-3.5 '-3
-3
-0.3
-0.3
-0.4
-0.4
-0.5
-0.5
^f-
10g(l)
log(l) log(i)
10g(l)
Figure C7:
Figure Potential Vs
CI: Potential Vs log Figure C8:
Figure Vs log |i|
C 8 : Potential Vs Iii
|i| graph
Iii graph for Test Test Id CuO 1-
CuOl- graph for Test
graph Test Id Cu09-01Fe09-
09FeOl-09HI5,
0 9 F e 0 1 - 0 9 H 1 5 , details of
of 01H15
0 1 H 1 5 ,, details of experiment are
of experiment
experiment
experiment are given given in given in
given in Table
Table 2.3.
Table
Table 2.3.
REFERENCES
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nd
Michael L. Free, Chemical
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Edition XanEdu
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Weed, The
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Copper, t h
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[ I I ] M.F.C. Carneiroa, V.A. Leao, Hydrometallurgy
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F. Zoueshtiagha,
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