Professional Documents
Culture Documents
Jalai Tajadod
Queen's University
Kingston, Ontario, Canada
June, 1997
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of Canada
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V w r Ne
Ournk,
votre ~ l e n m c e
Nom f d I m a
Efficient separation of enargite from other sulphide minerais is of great importance for
the metallurgicaf performance of flotation processes. This research was undertaken to
study the flotation chemistry of enargite in order to investigate the possible selective
depression of this mineral &om chalcopyrite in copper concentrates. To achieve this aim
adsorption and flotation characteristics of enargite and chalcopyrite using potassium amyl
xanthate (PAX) have been investigated. The effects of sodium cyanide, sodium sulphide.
potassium permanganate and aeration (air oxidation) as depressants on the adsorption
density of xanthate and floatability were studied.
It was found that the adsorption process on the enargite surface is independent of pH
in the range of 6 to 9 but decreases at higher pH values. The reaction of xanthate with the
oxidation products on the suditce of enargite through an ion-exchange process is
considered to be the major adsorption mechanism responsible for the xanthate flotation of
enargite. The surface species responsible for flotation of enargite based on electrochemicai
mode! theory and electronic structure of the solid adsorbent and infiared studies was
determined to be cuprous xanthate. Investigation of the effect of sodium cyanide showed
that cyanide decreased the adsorption density and the adsorbed xanthate was rapidly
removed fiom the enargite surface. Sodium sulphide had less depression effect than
cyanide on enargite. In the presence of oxidants the recovery of enargite decreased
remarkabl y.
The effecrs of NaCN and KMnOl on chalcopyrite showed that the adsorption density
and flotation recovery decreased with increasing concentrations of these ions. Sodium
sulphide had the strongest depression effect on chalcopyrite.
Depression of enargite fiom a bulk chalcopyrite-enargite concentrate at pH 9 was
achieved through the use of appropriate concentrations of sodium cyanide and potassium
permanganate. Aiternately, chalcopyrite was depressed by application of sodium sulphide
while floating enargite.
Eventually, efforts were made to develop a new and more selective depressant for
enargite without any impact on the environment. The separation of enargite and
chalcopyrite was achieved through the application of a newly developed depressant for
enargite by using a mumire of Magnesium Chloride. Ammonium Chloride and Ammonium
Hydroxide (MAA).
ACKNOWLEDGEMENT
The author wishes to express his appreciation to his s u p e ~ s o Professor
r
W. Tai Yen.
whose help and expert guidance were instrumentai throughout the course of this research.
investigation.
The author also wishes to thank the faculty, staff and graduate colleagues of the
Mining Department. Mr. Pat Muliigan of the Chernistry Department. M.. Charlie Cooney
of the Materials and Metallurgical Engineering Department and Mi. F. Bouzari of the
Geology Deparunent for their assistance and CO-operation.
Finally, the author is deeply indebted to his wife, son and daughter for their patience
and encouragement over the years it took to finish this project. The author thanks his
parents. sister and brothers for their generous suppon and encouragement during the
entire course of his education.
iii
TABLE OF CONTlENTS
Page
ABSTRXCT ............................................................................................................................................
.ACKNOLVLEDGEMENT.......................................................................................................................
ii
...
iii
CHAPTER L
[NTRODUCTION ................................................................................................................
L I T E R A R~ E ~ ............................
W
.
.
................................................................... 3
2.1 PROPERTESOF -TE
2 . 2 ~LECWISM
OF -TE
COLLECTORSFOR F L O A ~ SULPHIDE
G
M~NERALS
.......... 4
ADSORPTION
ON SULPHIDE
~ ~ ~ E R A.........................
L S
8
10
.
.
................................................ 10
15
2.4 E~.ECTRICU
ASPECTS OF XAMHATE CEMISORPTION ON SULPHIDE
MJNERALS ...... 16
2.4. 1 Electncal Double Layer ...................................................................................
16
3.5 ELEC-I-ROCHEMISTRY
OF SULPHIDE
M ~ M SFLOTA~ON
..............................
22
...... 27
.
,
2.6 MECE-IAMSM
OF ACTTON
OF DEPRESSANTS
ON SULPHIDE
MINERALS........................ 31
2.6.1 Depression of Sulphide Minerais by Sodium Cyanide ....................................... 32
2.6.2 Depression of Sulphide Minerals by Sodium Sulphide ...................................... 35
2.6.3 Depression of Sulphide Minerais by Oxidation ................................................. 37
3 2 PROCEDURES
......................................................................................................... 55
3 2 . 1 Adsorption ......................................................................................................
55
3 2 . 2 Flotation .......................................................................................................... 57
60
60
61
61
CHAPTER 4
FL(N.ATIONCHEMISTRY
OF S Y N T H ~ C ENARGITE
.......................................................... 63
4. 1
ReSUL.s ................................................................................................................
4.1.1
63
Adsorption ...................................................................................................... 63
73
88
41
93
94
4.2 DISCUSSION
........................................................................................................... 97
97
101
102
105
107
4 2 . 7 Effect of pH ........................
...
108
....................................................................
IO9
110
114
116
4 .3 CONCLUSIONS...................................................................................................... 117
CWTER5
FLOTAIION CHEMISTRY
OF N
AE N A ~
RG
..........................................................
~
120
5 1 RESULTS ..............................................................................................................
.
120
5.1.1.1
............................................................................
.
.
.
.
127
129
131
133
..............................................................................
6.1 RESULTS ...................... .
.
.
139
139
145
146
147
150
154
155
.........................................................................................................
6.2 Drscussro~
157
Adsorption ....................................................................................................
157
Flotation ......................................
158
159
160
J
Effect of K M ~ O........................................................................................
161
Effect of pH ........................ .
.
.
............................................................... 162
Effect of Aeration ...................................
.....................................................
163
163
CHAPTER 7
COMP.~RISON
OF m FLOTATIONCHEMISTRY
OF SYNTHETIC
ENARGITE
NA^ ENARGITE
AND CHALCOPYRITE
....................................................................
INTRODUCTION
166
....................................................................................................
166
167
7.1
175
.............................................
177
178
179
7.32
182
188
7.5 CONCLUSIONS
...................................................................................................... 189
CEUPTER 8
REDUCTON
OFTHE ARSENICCOMENTINCOPPERCONCENTRATES
......................-....... 191
191
......................................................................................
8.2 SEPARATIONFLOTAT~ON
193
197
8.3 CONCLUSIONS
......................................................................................................
199
SELECTIVEDEPRESSIONOF E N A R GBY
~ A ~GNESIUM-AMMON~UM
MIXTURE .......... 200
9 . i INTRODUCTION....................................................................................................
200
9.2 EXPERIMENTAL
TECHNIQUES
............................................................................... 200
9.3 RESULTS ............................................................................................................
201
201
9.4 DISCUSSION
.........................................................................................................
213
9.5 CONCLUSIONS
..................................................................................................
215
CELAPTER 10
SLJMMARY. CONCLUSIONSAND RECOMMENDA~ONS
FOR FUTURE STUDY ...................-217
1O.1
SWY
AND CONCLUSIONS
........................
-......
...................................... 2 17
10.2 RECO~IEM>ATIONSFORFUTURE
S ~ ...........................................................
Y
222
X-RAYD m c n o ANALYsIS
~
OFC-S
E N A R G............................................
~
230
Appendix A2
CALCULATION
OF ADSORPTIONDENSITY
...................................................................... 2; 3
Appendix A3
S WACE AREA DETERMINATIONS
............................................................................... 2; 4
Appendix A4
CXCULATIONOF MONOLAYER
FOR SYWHETICAND NATURAL
ENARGITE
AND
CWCOPYRITE ............................................................................................................
235
Appendix A5
C.UCI~ZATION
OF THE RECOVERY ................................................................................ 236
Appendix -46
PIJRIFIC'ATIONOF POTASSRIMAM-
-TE.
......................................................... 23 8
Appendix A7
RESULTS.................................................................... 242
LIST OF FIGURES
Page
Figure 2.4.1 : The structure and potential gradient of an electrical double layer. ............. 19
...~-.-...-.--.-..-................................................................
24
Figure 2.10 1a: Enargite composition in the Cu-As-S system in atom percentage. ........ .46
49
Figure 4.1 1c: Langmuir plot of C K versus C for the adsorption of xanthate
on synthetic enarsite...........................................-..........................................................66
Figure 4.1.1.1: The efEect of sodium cyanide concentration and contact tirne on the
pre-adsorbed xanthate on synthetic enargite at pH 9 and 20 mgll
..
in~tialPAX concentration............................................................................................... 69
Figure 4.1.1.2: The effect of sodium sulpkde concentration and contact time on the
pre-adsorbed xanthate on synthetic enargite at pH 9 and 20 mg/i initial PAX
concentration.................................................................................................................
Figure 4.1.13 : The effect of KMn04 concentration and contact time on the
pre-adsorbed xanthate on synthetic enargite at pH 9 and 20
70
...
73
74
80
Figure 4.1.2.2: The effect of sodium sulphide concentration and contact time on the
floatability of synthetic enargite at pH 9 and 20 mg/l PAX concentration. ...................... 8 1
Figure 4.1.2.3a: The effect of flotation pH and pH regdators on the floatability of
synthetic enar~iteat 20 mgil PAX concentration ...........................................................
82
83
...................................................
85
87
Figure 4.1 .z.7: Relationship between flotation recovery and pulp potential for synthetic
88
90
Figure 4.1 Ac: The effect of NaCN concentration on the contact angle of synthetic
enargite i t 20 m g P A X concentration ......................................................................... 92
Figure 4.1.7: Determination of zero point of charge of synthetic enargite using the
adsorption of potential determinhg ions technique......................................................... 95
Figure 5.1. la: The adsorption of PAX on natural enargite as a function of t h e at
20 m g initial xanthate concentration........................................................................... 120
Figure 5.1.1.2: The effect of sodium sulphide concentration and contact time on the
pre-adsorbed*xanthateon natural enargite at pH 9 and 20 mgIl PAX concentration....... 124
Figure 5.1 . 1.3. The effect of K M ~ Oconcentration
J
and contact time on the
131
174
Figure 7.2.3: The effect of KMn04 contact time on the pre-adsorbed xanthate on
minerals at pH 9, 20 mg11 PAX and 50 mg/l KMnOJ concentration. ......................... 175
Figure 7.2.4: The effect of pH on the adsorption density of PAX on rninerals at
20 mg/l PAX concentration. ..................... .
.
.
......................................................... 177
Figure 7.3 : Floatability of synthetic enargite, natural enargite and chaicopyrite at pH 9 178
Figure 7.3.1 : The effect of NaCN contact time on the floatability of rninerals at pH 9,
20 mg/l P.4X and 15 mg/l NaCN concentrations. ........................................................
180
Figure 7 3.2: The effect of sodium sulphide contact time on the floatability of minerals
at
pH 9, 20 mg/I PAX concentration and 10 mg11 sodium sulphide concentration. ........ 182
188
Figure 8.2.3: Copper recovery versus arsenic recovery at 4.75% As in feed sample. .... 198
206
Figure 9.3.3a: The effect of surface tension regulated by rmthanol on the floatability
Table 8.1 : Separation flotation tests for the mixture of enargite and chalcopyrite
at 4.75% As in feed sample.......................................................................................... 196
Table 9.1 : The effect of MAA conditioning tirne on the adsorption density of
synthetic and naturai enargite....................................................................................... 202
Table 9.2: The effect of MAA on the floatability of synthetic enargite
naniral enargite and chalcopyrite.................................................................................. 208
Table 9.3: Separation flotation tests for the muctUre of enargite and chalcopyrite
-0
at 1 . 7
/O
~ As in feed sarnple.......................................................................................... 211
LIST OF ABBREVLATIONS
PAX
PEX
MAA
Min.
Minute
vs.
Versus
Ave.
Average
Conc.
Concentration
Equil.
Equilibrium
Recovery
SCE
S E
Vol.
Volume
ZPC
Zero Point-of-Charge
sis
CHAPTER 1
Introduction
Arsenic is the 20th most abundant element in the earth's crust ar a level of about 2
ppm. It is a constituent of over 300 minerais and is comrnoniy found in non-ferrous ores
such as copper. lead. zinc. gold and uranium. Many copper sulphide ores contain arsenic
in the form of enargite (Cu3AsS4). Froth flotation processes invariably concentrate
enargite aion%with chaicopyrite and other copper sulphides. The presence of arsenic not
only makes a concentrate unsuitable for funher chemical and metallurgical processes. but
also creates environmental problems. Arsenic is a major pollutant of copper
electrowinning solutions and leachates (Lorenzen et al. 1995). In almost ail cases. it is an
unwanted impunty and can cause concern due to its potential impact on process chernistry
and environment (Langhans et al. 1995). Therefore. it is necessary to reduce arsenic in
copper concentrates and at the same time to maintain a satisfactory recovery of copper.
The purpose of this study was twofold. First, to study the flotation chemistry of
enargite because no previous research had been undertaken on this mineral. Secondly. to
reduce the arsenic content of copper concentrates by the fioth flotation technique. In the
field of mineral processing, there are no documents reporting the flotation of enargite and
its separation tom
pyrometaiiurgical and
tests in the presence and absence of activators and depressants for the synthetic enargitexanthate system and discusses the mechanisms involved. The same investigation was also
conducted for the chalcopyrite-xanthate system in order to compare the flotation
behaviour of these minerals. These studies were intended to establish the possibility of
selective depression of enargite. To avoid the effect of impurities, this investigation was
limited to a simple system involving pure minerals, pure xanthates. depressants and pHregulating agents. Synthetic enargite was used throughout this study because impunties in
naturd sarnples would affect the original properties of enargite. However. additional
expenments using a selected natural enargte sample were also conducted to compare with
synthetic enargite.
In seiective depression of enargite from chalcopynte, both minerals were preconditioned in ~anthatesolution followed by conditioning with depressants and flotation.
The reverse pre-conditionhg sequence was aiso conducted. Several common depressants
such as sodium cyanide, sodium sulphide and potassium permanganate were used in the
investigation.
Finally, since these depressants would not produce an acceptable seiectivity for
chalcopyrite and enargite, magnesium-ammonium mixture was selected to effectively
separate enargite and chalcopynte.
CHAPTER 2
Literature Review
Froth flotation has become one of the most widely applied processes for treating
sulphide minerals since the introduction of xanthates because of its simplicity and relative
low cost. The flotation process is a means whereby minerals are separated fkom each other
or From their associated rock gangue. This process involves the chemical treatment of the
aqueous ore pulp containing discrete particles of vaiuable and waste minerals. The
chernical treatment with a collector is the means by which the surface of the valuable
constituent is rendered hydrophobic. This enables the rnineral of interest to adhere to the
air bubbles introduced into the pulp and to be carried to the surface where it can be
collected as a concentrate. Depressants are chernicals that either prevent the adsorption of
a collector on a specific minerai or remove a coilector film which has already been formed
on the rnineral. Frothers are required in flotation to promote the formation of a fioth phase
on the surface of the pulp. Another class of reagents called activators. are chernicals which
promote the action of collector adsorption on rnineral particles. pH regulators are also
used in flotation because pH regulation is a major controlling factor in the separation of
minerals. The presence of three phases, solid, liquid, and gas is necessary for the flotation
process to occur.
The fundamental mechanisms controlling the flotation process beiong to the rather
complex field of surface chemistry since different reagents interact with the rnineral
surface in an aqueous medium. Surface properties play an essential role in Botation. In
and the effect of depressant deals with the solid-liquid interaction, the present
investigation is concemed with reaction at the solid-liquid interface. This review is limited
to the propenies of collectors. depressants, minerals and their interface.
Surfactants which act as collectors adsorb at the solid/liquid interface and make the
surface of seiected minerals hydrophobic in character. Collectors are heterogeneous
cornpounds that contain a functional inorganic group coupled with a hydrocarbon chain.
They possess at Ieast one nonpolar and one polar portion. Owing to chernical, electrical.
or physical attraction between the polar portions and the surface sites, the collector
adsorbs on the panicles with their nonpolar ends oriented towards the bulk solution.
thereby imparting hydrophobicity to the particles (Somasundaran 1975). In other words.
the inorganic group is the portion of the collector molecule that adsorbs on the mineral
surface, while the hydrocarbon chain, being non-ionic in nature, provides hydrophobicity
to
the rnineral surface as a result of collector adsorption. Collectors are classified on the
basis of composition and whether they exist as cations, anions or molecular species in
solution (Fuerstenau et al. 1985).
Xanthates, or aikyl dithiocarbonates, the most cornrnonly used sulphydryl anionic
collectors, are cumently employed as collectors in the flotation benefication of most
suiphide ores. Xanthates are manufactured From a reaction between the appropriate
alcohol. carbon disulphide and the appropriate hydroxide as follows:
ROH+ KOH + ROK +H20
4 alkyl alcohol
potassium alcoholate
ROK
- CS2
+
P
(2.1.1)
ROCSzK
(2.1.2)
.1
R-O-C-S-K
II
'r
Anion 6Cation
.ilkali metal xanthates. ROCS&l (M. alkali metal & R=C,H2,-1, hydrocarbon radical).
with shon hydrocarbon chain (C2-CI). as employed in flotation technology. are hizhly
soluble in water and are completely dissociated into xanthate anions and metal cations.
Longer chained molecules tend to be more selective but less soluble. Aqueous xanthate
solutions are fairly stable in neutral and alkaline pH regions but rapidly decompose in acid
solutions into carbon disulphide and alcohol and their use is restricted to alkaline pulps.
Xanthate adsorption however, is reduced at high pH levels because of cornpetition from
hydroxyl ion adsorption. Their decornposition is generally considered to proceed via a
hydrolysis :
(2.1.3)
decomposition:
ROCS2H
+
* xanthic acid
(2.1.4)
ROH + CS2
+ aicohol
+ carbon disulphide
molecules of water of crystallization and are therefore less stable (Crozier 1992).
On the other hand, heavy metal xanthates are relatively insoluble salts f o n e d by
reactions between xanthate anions and heavy metal cations in solution. a fact of great
importance in the explanation of the xanthate adsorption mechanism. Their aqueous
solubility appears to be closely related to the degree of covalency of the metal-sulphur
bond and to the valency of the metal atom. For example, the higNy covalent monovalent
metal xanthates of Hg, Au, Cu and Ag are the least soluble (solubility products, Ksp
loJU - IO-"), while Pb and Zn xanthates are much more soluble (Ksp
= 10-l~
10"').
Solubility products of the metal xanthates cm be noted to decrease with increased chain
In acid solutions, or under oxidizing conditions, alkali metal xanthates are easily
decomposed to give a vanety of compounds of which the most important one is
dixanthogen, a highly insoluble oil, which reduces the selectivity of collecter. Structurally
dixanthogen may be written as the combination of two xanthate radicals according to:
R-O-C-S-S-C-O-R
II
In the precipitation of metal xanthate salts in solution, the stoichiornetry of the metal
salt is generally two to one for divalent metal ions. For exarnple. lead ethyl xanthate is
Pb(EX)2,S,where E X represents ethyl xanthate ion. In the case of cupnc ion, however.
oxidation of xanthate to dixanthogen by CU'& occurs dunng which cu2- reduction to Cutakes place. Cuprous xanthate, being very insoluble, forrns by precipitation by the
following reaction:
CU'-
+ 2EX
+ CUE&~,
+ 1/2(EX)2
(2.1.5)
where E X and (EX)* represent ethyl xanthate and diethyl dkanthogen, respectively. In
this case. essentially complete oxidation of xanthate is effeaed up to pH 10. .Mthough
cupric xanthate foms initially in this system, it is not a stable species. and its existence is
only temporary. In addition to oxidation by cupnc ion. xanthate can also be oxidized to
the dimer, dixanthogen, by femc ion and dissolved oxygen. The oxidation reactions are:
2X +- 2 ~ e ' -+ 2 ~ e +~Xz
-
(2.1.6)
(2. I .7)
Oxidation of xanthate by femc ion does not occur at pH 6 and above. Athough xanthate
oxidation by dissolved oxygen is thermodynarnically favourable, it is slow kineticaily As a
result dixanthogen formation in this manner can be assumed not to occur to any
(Poling 1976). The formation of dkanthogen in aqueous solutions may be beneficial to the
collecting action of xanthate. It has been s h o w that dixanthogen piays a crucial role in the
adsorption of xanthate on sulphide rninerals (Fuerstenau et al. 1968). With regard to
dixanthogen stability, it is important to note that dixanthogen is not stable above about pH
10.5. Xanthate ion is the stable species under these conditions (Fuerstenau et al. 1985).
In physical adsorption, the adsorption takes place in the outer double layer through
such forces as electrostatic attraction and through hydrophobic bonding (van der Waals'
interaction between hydrocarbon chahs). This means that any ions may be adsorbed.
regardless of their nature, dimensions, and size of charge, since ody the overali electrical
balance is important. Consequently physical adsorption cannot be selective in relation to
the soiid.
Since the introduction of xanthates as sulphide collectors many theories have been
postulated to explain their action. The action of xanthates in rendering sulphide mineral
surfaces hydrophobic is explained in general terms by chemisorption of the xanthate on the
originally hydrophilic surface through its dithiocarbonate polar group, leaving the
hydrocarbon chain extended away from the surface. In other words. the adsorbent must
contain chernical eiements which actively interact with the sulphur atom in the xanthate
polar group. When the surface becomes covered with a sufficiently dense coating of these
oriented molecules (significantly less than a monolayer) the surface becornes panially
hydrophobic and the mineral particle becomes floatable (Poling 1963 ). The surface
reaction products which are formed when sulphide minerals react with xanthates were
analyzed by .Mison et a1 ( 1972) using spectrophotometric methods. These products were
found to be predominantly either metal xanthate or dixanthogen, depending on the
panicular sulphide mineral. The nature of the reaction products does not Vary with pH of
the solution nor with the chah length of the xanthate homologue used.
2.2.1
negatively charged ions of xanthate through this potential barrier would be impossible. A
theory was proposed whereby an uncharged molecule such as xanthic acid was considered
to be the effective adsorbing species. The neutral molecule theory of Cook and Nixon is
based on the hydrolysis of xanthate to xanthic acid in solution. According to this theory.
xanthic acid is necessary to form and split out water by combination of hydrogen ions
from xanthic acid and adsorbed hydroxyl. They considered the effective colleaor to be a
non-ionic species derived from hydrolysis of the ionized collecter in solution. Their
original argument for this theory was based on the higher surface activity of neutral
heteropolar molecules than that of ionized molecules, as a result of electrical double layer
consideration. They were not specific as to whether the adsorbed species remained as
undissociated xanthic acid (for alkali metd xanthate collectors) or whether this species
reacted with the surface to produce a metal xanthate surface compound. The neutral
molecule theory is in disfavour since electrostatic repulsion effects might contribute oniy 3
to 4 percent of the total chemisorption energy (Poling 1976). Fuerstenau et al. (1990)
stated that negatively charged xanthate ion could adsorb by specific chernicd interaction
above the zero point of charge. under which condition the mineral surface is negatively
charged.
Sutherland and Wark (1955) and later Gaudin (1957) proposed an adsorption
mechanism which has probably received the widest acceptance. They proposed ihat. since
xanthate anions are by far the most predominant species in solution, these anions adsorb
on sulphide surfaces by exchange with previously adsorbed anions. This included adsorbed
ions such as hydroxide or carbonate, and ions formed by oxidation of the sulphide mineral,
such as sulphate or thiosulphate. For instance, if the sulphide surface oxidizes to
thiosulphate, the following reactions can occur:
(2.2.3.1)
and:
MS20;+ ZROCSI- + M(ROCS2)2+ ~
2 0 3 ~ '
(2.2.3-2)
or anodic reaction:
Z M S +4ROCS<+31&0
+ 2M(ROCS2)z+~2032-+6K+8e*(2.2.3.3)
This theory of exchange adsorption accounts for the orientation of the xanthate film, one
part (polar group) of which is attached to the mineral surface and the other part of which
points away from it. Such orientation cannot be expected in normal chernical compounds.
Sutherland and Wark developed the ion exchange theory on the bais that suiphides are
usually floated with less than monolayer coverage. Gaudin and Preller (1946) reported
that typical. practical coating usually amounted to much less than the equivaient of a
complete monolayer coverage. They did this study on the basis of mil1 records on collector
consurnption. In the laboratory, collector coverage can ofien far exceed that required for a
single. close-packed monolayer if the sulphide rninerals are either heavily oxidized or if
dissolved oxygen is conrinually available duing the adsorption process (Poling 1976).
This theory attributes the creation of a hydrophobic film on the rnineral surface to an
exchange adsorption between xanthate ions in solution and lattice ions held in the
electrical double layer of the rnineral surface.
Studies of the kinetic laws of reagent adsorption in different conditions have shown
that the collector adsorption by sulphide rninerals proceed according to equations of the
following type (Bogdanov et al. 1960):
T=at1"
(2.2.3.4)
or:
r = b + ai log t
(2.2.3.5)
where:
r is the arnount of reagent adsorbed by a unit minerai surface area during the time t.
and a
n. b and ai are constant values. However, the empiricai equations given contain no explicit
relation between the rate of the process and the reagent concentration in solution, which
rnust determine the kinetics of the process.
Generaily speaking, the actual order of a complex reaction may have any value differing
from the stoichiometric value, but it is usually smaller than the latter. In many cases of
heterogeneous chernical reactions, involving an exchange between A-ions of the mineral
surface and B-ions of the reagent in solution, however, a linear relationship is observed to
exist between the rate of the process and the reagent concentration in the solution. Thus:
df/dt = kS.xCB- kISsC.+
(2.2.3.6)
where:
S, is the fraction of the surface, occupied by A-ions;
Cg are the concentrations of the corresponding ions in the solution; and k and k ,
are constants characterizing the fixation of A-ions and B-ions on the mineral surface.
At equilibrium, the second terni at the nght side of equation (2.2.3-6)equals the first term,
and dl7dt = 0, but if the adsorbed ions are fixed on the surface more firmly than the ions
displaced by thern (k >> kl), then at any adsorption values, even those close to the
equilibrium. ~ S A C B>> klSBC.A, and the second term of equation (2.2.3.6) may be
neglected.
Experimental data obtained by Bogdanov et al. (1960) on the kinetics of interaction
between xanthate and galena and between Cu-ions and sphaierite (in both cases ar
adsorption values. constituting fractions of a monolayer) satisQ the equation:
drldt = kS.4CB
(2.2.3-7)
Electrochemical model theory was developed by Plaksin and Shafeev (1963). Tolun
and Kitchener (1964), Majima and Takeda (1968), Mison et al. (1972). Woods ( 1976).
Richardson et al. (1984) and Chander (1988). With regard to the electrochernical modei.
when a sulphide mineral is placed in an aqueous solution. the mineral develops a potential
termed the rest potential. When the rest potential is greater than the reversible or Nernst
potential for xanthate oxidation. xanthate is oxidized electrochemically to dixanthogen on
the mineral surface. while oxygen is discharged to hydroxyl. Pyrite, arsenopynte and
pyrrhotite fa11 into this category in the presence of ethyl xanthate (Allison et al. 1972).
When the Test potential is cathodic or less than the reversible xanthate/dixanthogen
potential, oxidation of xanthate cm not occur, and metal xanthates are observed on the
sulphide surface.
The role of oxygen in collecter adsorption on sulphides has been described by many
investigators. Most investigators (e.g., Gaudin 1957, Woods 1976) have stated that the
presence of oxygen is mandatory for thiol coiiector adsorption. They agree that in the
absence of oxygen, sulphide minerals will not Boat using xanthates as collectors. Water.
open to the atmosphere, is nomally saturated with oxygen to the extent of 8 mg1 at room
temperature (Nakazawa and Iwasaki 1986) so that under these conditions there is dways
a plentiful supply of oxygen available. Attempts to completely exclude oxygen from a
surface or aqueous adsorbate solutions are near impossible and it can therefore be safely
assurned that the surface is covered by at least a partial monoiayer of adsorbed oxygen.
Studies on the effect of dissolved oxygen have considered its interaction with the mineral
surface (adsorbent) and its interaction with the xanthate (adsorbate).
Since sulphide minerals are readily oxidized, most theories propose that oxygen alters
the sulphide surface to a metal-sulphur-oxygen surface compound. The solubilities of
sulphide minerals in water are very low, suggesting that sulphides should be relatively inen
in aqueous solution. However, they are therrnodynamicaily unstable in the presence of
s*-, ~ 2 0 3 and
~ -
~0:'
conditions. Surface analysis by ESCA and Auger Spectroscopy have provided direct
expenmental evidence of this phenornenon (Clifford et al. 1975). These oxidation products
are more soluble than the parent sulphide minera1 and therefore metd cations are made
more readily available for interaction with xanthate collectors by an ion-exchange process.
Oxidation of sulphide surfaces does not proceed unifonnly over the entire surface and this
represents one cause of the electrochemical heterogeneity of these surfaces. The oxygen
mechanism has been proven to be thermodynamicaily feasible and is rapid at basic pH
levels (Fuerstenau et al. 1971). Gaudin et al. (1956) have shown that monolayer coverage
on pyrite is exceeded oniy in the presence of oxygen. Although oxygen is essential to the
notation of sulphide minerals and this concept has been supported by much experimental
work an excessive exposure of sulphides to oxygen cm adversely affect their
floatabilities.
As mentioned earlier, xanthate oxidation to dixanthogen in solution may play a role in
the interaction between sulphide minerais and xanthates. Gaudin et aL(1934) have
rnentioned that the xanthate ion oxidizes readily to dixanthogen in the presence of oxygen.
Xanthates may first go to dixanthogen and the latter may react with the rnineral, or the
combined reaction of xanthate, the sulphide minerai and oxygen may take place at the
surface of the mineral. Klymowsky and Salman (1970) have stated that the role of oxygen
in xanthate flotation is to oxidize the xanthate ions to dixanthogen to permit the collecter
The surface of any solid or liquid phase differs fiom the interior in that there is not a
complete balance of inter-rnolecular forces at the surface. When rnineral particles are
immersed in an aqueous medium they acquire a net surface charge characteristic of that
particular mineral due to preferential dissolution of surface ions as discussed by de Bruyn
and Agar (1962). When the solid is imrnersed in water the electrical balance at the surface
is disturbed by the passage of metal ions from the surface into the solution. To achieve
electncal neutrality, oppositely charged ions mua be adsorbed onto the surface from the
surface charge with respect to the solution. The surface charge is compensated by an
equd charge distribution in the aqueous phase. The charge in solution together with the
charge on the sulphide mineral surface is referred to as the electrical double layer.
The first model of the electrical double layer originated with Helmholtz (1879) and
Perrin (1904). Some years later, Gouy (1910) and Chapman (1913) independently
suggested the modem mode1 of the structure of the electncal double layer (Leja 1982).
Helmholtz originally proposed that the potential difference between two phases resided in
two layers of charges of opposite signs; that is. a layer of positive ions irnmediately
adjacent to a negatively charged surface. Gouy and Chapman recognized that the like
charges on the solution side of the interface would attract unlike charses causing a
disturbance or diffuse charge distribution. The Gouy-Chapman theory of the electncal
double layer predicted an excessively high concentration of ions near the solid surface
mainly due to a neglect of the finite sizes of ions. Later Stem (1924) recognized that the
specific adsorption of ions and their finite sizes could lead to a formation of an inner
compact layer of ions at the surface with a second diffuse layer extending into the liquid
phase. The Stem model of the double layer c m be considered to be composed of a
combination of the Helmholtz and Gouy models. Figure 2.4.1 showsathe structure of a
double electnc layer in which it is assumed that surface cations pass into solution. Because
of the surface charge, ions of opposite charge in solution will be attracted towards the
surface. There will therefore be a higher concentration of counter-ions close to the
surface, than in the bulk of the liquid. This concentration faiis off with increasing distance
From the particle, so that there is a bound layer of counter-ions at the particle surface.
succeeded by a more diffise layer. Beyond the difise layer is the bulk solution, in which
the ionic distribution is random. The bound layer rnoves with the particle, as the latter
travels through the medium, so that there is a plane of shear between the bound and
diffise layers. The potential difference between the plane of shear and the biilk solution is
the zeta potential. The potential
point close to the particle is still ni1 at C, but it increases rapidly up to B. At this point it is
known as the electrokinetic, or zeta potential
(6). The 5
determined more easily than the actual surface charge, is often a convenient measure of
that charge. Most zeta potentiai determinations rely on electrophoretic methods, and
measure the rnobility of individual charged, suspended particles under the influence of an
applied potentiai. The zeta potential is calculateci from the foilowing relationship
(Fuerstenau et al 1985):
< = 4 x r r x ( p / D ) x ( V / E ) x 9 x 10''
where:
= zeta potential, volt
(2.4.1.1)
D = dielectric constant
V = pmicle velociry, c d s e c
Plane ofs
Figure 2.4.1: The structure and potential gradient of an electrical double layer.
2.41.1
Studies of mineral double layer characteristics have been useful in understanding the
collecter adsorption mechanisms in flotation systems. As mentioned earlier, most base
rnetai sulphides take on a net negative charge in water due to preferential dissolution of
meral cations from the surface. Upon addition of a high concentration of metal cations to
the solution phase, a net transfer of cations tiom the solution to the solid will again lead to
equiiibnum and the sulphide could then be positively charged. The metal cation c o m o n
to the metal sulphide is therefore called a potential determining ion. Similarly, the sulphide
ion or hydrosulphide ion is a potentiai determining ion for this system and the addition of
soluble sulphides to the solution can make the potential of the sulphide mineral more
negative or cathodic. The use of Na2S as a depressant in xanthate collection of sulphides
is well known and is jenerally ascribed to adsorption of the HS- ion. It is reasonable to
expect thar in making the surface more cathodic. xanthate anions and even neutral dipolar
xanthate species would be more strongly repelled from the interface. Hydrogen ions and
the hydroxyl ion cm also be considered potential determining ions since they take part in
anv- hvdrolysis
.
reaction; (Le. S= + K + HS3. pH regdation has long been recognized as
potential carried by the sulphide surface). Plaksin's resulrs (1960) on the exclusion of
xanthate From surface regions which were oniy about 200 m V more cathodic than micro
regions showing active xanthate adsorption, confirm that the xanthate adsorption process
is very sensitive to surface potential variations. If the adsorbing species were a neutral
dipolar type molecule whose polar group camied only a fiaction of the electronic charge,
the potential barrier would be signdcantly Iowered and its adsorption should be favoured.
Surface potential variations could still govem the adsorption due to the dipolar nature of
these molecules. On this basis, any reduction in the cathodic potential of a minerai surface
should favour the adsorption of dipolar molecules more than that of colIector anions.
In flotation chernistry research, the adsorption of organic and inorganic ions at the
(F), which is at a distance of closest approach of counter ions to the surtace, 1s gven by
the Stem-Graham equation (Somasundaran 1975):
(2.4.1.1.1)
where r is the effective radius of the adsorbed ion, C is the bulk concentration in rnol/cm3.
A G o 3is~ the standard free energy of adsorption, R is the gas constant, and T the absolute
is the driving force for adsorption and cm be considered to be made
temperature. AGoZdr
up of a number of terms, each term for a given type of interaction that is responsible for
the adsorption:
(2.4.1.1.2)
AGcla is the electrostatic interaction term equai to zFy6 where z is the vaiency of the
AGoCh,, is the chemicai term due to any covalent bond formation between adsorbate and
adsorbent; AG0,, is due to the cohesive chain-chah interaction that couId occur between
the surfactant species upon adsorption; AG0,, is similar to AG0=, and is the van der Waals'
hydrophobie
Many metal sulphides and metai oxides are semiconductors, substances which possess
two types of charge carriers; electrons in the conduction band and holes in the valence
b e ~ e e nthat of metals and insulators (Hamy 1960). Metals and semiconductors have
distinctly different elecuical and electrochemical properties. These dserences arise
primdy because the charge carrier concentrations of semiconductors are much lower
than in metais, 10"- 10l6per cm3 as compared to l0*-10~~per cm3in metals where only
the electrons are charge caniers (Leja 1982). In addition, the electron carriers in
semiconductors cm occupy only certain energy bands or levels. The conductivity of most
metais is of the order of 10'-10~ n'lem" and is entirely due to the high concentration of
electrons. Semiconductors have conductivities orders of magnitude lower than those of
rnetals, namely in the range of 10.'- 1O"> ~''crn-'. Insulators have conductivities lower than
1O-''
CPcrn-' .
Establishment of an electncal double layer at a solidAiquid interface results in a
potential variation which extends not only into the solution phase, but dso into the solid.
The double layer enension into a metal is generally ignored because it can only extend
into the solid perhaps 1 or 2 atomic layers at the most. In the case of semiconductors.
surface charge transfer in adsorption processes can extend the interfacial electric field to a
layer depth into the solid. In some serniconductor studies, surface effects can completely
dominate the electronic properties of the material.
carbons, dl of the electrons are used up in forming the covalent bonds. In this situation no
net flow of electrons through the solid is possible, and the material is an insulator.
If an extra electron is added to the structure, however, no empty bonds are available,
and the electron is free to wander through the solid. It wili move through the crystal in the
opposite direction from an applied electric field, and can thus contnbute to the electricai
conductivity. This situation is shown in Figure 2.4.2a(b). Electrons which are not bound in
the valence bands, and are thus free to rnove in this way, are called condudon electrons.
If conduction electrons can be produced in some manner in sufficient quantity, the matenai
There is a second way in which the total number of electrons fails to match the number of
available bonding sites, Le., when there are too few electrons. There is then only one
electron in some of the bands, as shown in Figure 2.4.2a(c). This missing banding electron
is called a "hole". It, like the conduction electron, is eee to wander through the crystal. As
shown in Figure 2.4.2a(d), an electron in a band adjacent to the one-electron band where
the hole is localized, can jump into the empty position, leaving a vacancy behind as it goes.
.As this process is repeated, the net effect is for the hole to move through the crystal under
the influence of an electric field. It cm be seen that the hole wilI move in the opposite
direction from the conduction electron, since the motion of the hole is opposite to that of
the valence electrons. It thus behaves as though it were a positively charged particle, and
for this reason has often been called a "positive hole." We note then that the conduction
electron consistutes a local negative charge, and the hole a localized net positive charge.
Intnnsic semiconductors (such as germanium, silicon and tellunum) are electronic
conducting materiais whose conduction bands are separated from filled valence bands by
forbidden energy gaps of the order of the thermal energy kT (where k is the Boltzmann
constant and T is the absolute temperature) (Figure 2.4.2b). They are therefore essentially
insulators at low temperatures; as their temperature is increased. their electncal
conductivity increases which is opposite to the behaviour of metallic conductors. The
conduction process in intrinsic semiconductors involves excitation of electrons from the
fiiled vdence band to the empty conduction band thereby creating two mobile carriers,
namely: an electron in the conduction band and a "hole" in the valence band. The carriers
of electric charge may either be free electrons in the conductivity zone or free electron
vacancies (holes) in the valency zone. Owing to the statistical nature of the electronic
structure of semiconductors, the Fermi energy level, EF, best characterizes the electronic
potential enegies. EF denotes an energy level which has a probability of being occupied
equal to one half; therefore EF Lies in the forbidden energy gap. ln chemicai terminolog
the Fermi energy is equivalent to the chernicd potential of the electrons in the
serniconductor.
Extrinsic semiconductors owe their properties to the presence of trace impurities
(impurity-activated or doped) which create energy levels within the forbidden gap. If the
impurities bnng in extra electrons, they produce donor levels, ED,close to the conduction
band. Electrons fkom these donor levels are readily excited into the conduction band and
the solid is called electron-conducting or "n" type (minerals with free electrons). I f the
irnpurities absorb electrons from the lattice, they create acceptor levels,
EA,
near the
valence band. Electrons excited from the valence band to the acceptor sites are bound
there, but the "holes" lefi behind in the valence band are mobile and cm conduct. These
are denoted "p" type (minerais with fkee holes) semiconductors. Most semiconducting ore
minerals are extrinsic; enargite and chalcopyrite are examples.
Plaksin ( 1959) based the xanthate sulphide theory on the fact that sulphides are semi-
conduaors and have in many cases both elecaic and gap conductivity. The mineral urface
may therefore be considered as a composition of anodic and cathodic sites. Xanthate ions
will readily adsorb at the anodic sites where a strong chernical bond will be forrned by the
transitions of an anion electron into the Eee vacant situation in the sulphide mineral. At the
cathodic sites however, the increased electron concentration in the mineral sets up a
potential banier preventing attachent of collector anions. He proposed that oxygen
molecules adsorbed on the minera1 surface during the ionization process takes up the free
electrons which reduces the potential bamer and creates favourable conditions for
collector anion attachrnent.
&en
been considered that the mineral surface must first be oxidized to a metal oxy-
sulphur species which then exchange with collector ions in solution to forrn a metal
collector compound. The application of electrochemical concepts explains the production
of a range of surface species and demonstrates how the collector and oxygen can interact
simultaneously at the mineral surface.
The electrochernical theory of the action of thiol colleetors has been extracted from an
electrochernical theory of corrosion. This theory predicts that in order for a system to
remain electrically neutral, the surn of the rates of all oxidation reactions must equal the
When two electrodes in a ceU are connected by a metallic wire, an electric current will
Bow. Each electrode involves an electronic and electrolytic conduaor in contact. At the
interface between these two phases, there exists a potential dserence, called the electrode
potential. An electrochemical readon consists of a pair of oxidation and reduction
be split into haif reactions indicating the mode of electron transfer. In general, a half-
(2.5.1)
where EOis Standard Reduction Potential for species A" .and ah* and a,. are the
activities of the electron acceptor and electron donor, respectively, R is the gas constant, T
is the absolute temperature, n is the number of electrochemicai equivaients per mole, and
F is the Faraday constant (96500 Coulombs or 23.06 Kcal). The Nemst equation defines
the potential of the oxidized/reduced electrode versus SHE as a function of the activities
or concentrations of oxidized and reduced forms of the system.
The more positive Eh is, the more oxidigng the measured system relative to the
which can be measured by an indicator electrode. This is ody true when a redox couple
reversible to the electrode materiai is dominant. Thermodynamic reversibility impiies a
state of equilibrium at every state. For an equilibrium system, all the reversible potentials
of stable species may be depicted as relations of potentials and pH in Eh-pH diagrams.
It is therefore customary to represent the thermodynamic data of a mineral in collecter
solution in the form of an Eh-pH diagram. Such a d i a g r a . showing stability domains of
various species, is very valuable for determining the range of Eh and pH values in which a
hydrophobie species might form. Eh-pH diagrams can also be drawn for flotation
such as platinum and gold, are usefbl because they are good electron-transfer media. X
saturated calomel electrode is the most commoniy used reference electrode and it is a
common practice to report the measured potentials on the hydrogen scale by adding 0.242
V to the potentials rneasured with respect to the saturated calomel elecrrode (Chander
1988). Woods (1984) suggested that an electrode constmcted tom the mineral being
concentrated should make the most appropnate electrode for Eh measurements because
the relevant Eh is established at the mineraVsolution interface. If measurements are made
without passage of a current through the electrode, the rneasured potential is called the
rest potential of the mineral. The rest potential measurements can be used-to ascertain the
It is well known that rnetal sulphides are floated effectively in the presence of oxygen
with short-chah sulphydryl coffeaors. Xanthate collectors are most commody used in
sulphide flotation. A traditional mode1 for the mechanism of sulphide mineral flotation is
chemical adsorption. With the developrnent of eiectrochernical theory, a rnodel combining
mixed potential dong with chemicai adsorption, has become more widely accepted. In
general, sulphide minerals are semiconductors, and they c m act as an electron donor or
acceptor. Although surface phenornena in flotation may be interpreted to consist of simply
anodic and cathodic reactions. they usually involve more complex interactions of chemical
(2.5.1.1)
while the anodic processes are one or al1 of the following reactions (Cheng and Iwasah
1992):
a) Chernisorption
X = Xa& + e-
(2.5.1.3)
Formation of dixanthogen
3X = X2+ 2e'
(2.5.1.4)
a mineral or the formation of hydrophilic surtace speties such as hydroxides can depress
sulphide minerals. Hence, in the presence of xanthate, adsorbed xanthate (Xah),
dixanthogen (Xz)or rnetal xanthate (MXz) is responsible for sulphide minera1 flotation.
Apparently, al1 rninerals on which dixanthogen is formed have rea potentials in excess of
the equilibrium potential of the dixanthogedxanthate couple (reaction 2.5.1.4), and those
on which the metal xanthate is formed have potentials below this value. This contirms the
view that the oxidation of xanthate by oxygen at sulphide mineral surfaces is govemed by
Reagents that prevent the adsorption of collectors on sulphide rninerals and thereby
retard their flotation or rernove a collector film which has already been fomed on the
mineral, are known as depressants. The xanthates made notation of the sulphides fkom the
gangue minerals relatively straightfonvard. Attention was concentrated, therefore on ways
of floating one sulphide mineral away from another in combination with the xanthate to
selectively separate the suiphides from each other. The reagents used are chiefly inorganic
sdts which compete with the coUector for position on the sulphide surface.
The action of depressants is ememely complex and varied. The action may involve
the formation of a surface film snilar to the xanthate rnechanism, or it rnay be restncted
to adsorption of ions in the outer layer of the double elecvicai layer. The overd effect is
to produce conditions which impede or check collector attachent to the muieral. Some
depressants readily remove collector already attached to the minerai surface. Many
reagents are used in notation as depressants, however, the following discussion will be
limited to the action of sodium cyanide, sodium sulphide and potassium permanganate.
Sodium cyanide is probably the rnost commonly used reagent to bring about the
selective separation of many complex rnineral systerns. By suitable adjustment of other
of free cyanide ions to react and f o m compounds with heavy metal cations. This reaction
occurs in two stages. Precipitates of relatively insoluble cyanide salts are formed first, then
these salts dissolve due to the formation of cyanide cornplex ions by excess cyanide ion. In
the presence of free cyanide ions. the greater the solubility of a metal xanthate in cyanide,
the less stable will be the attachent of the collector to the surface of the corresponding
mineral.
This, however, only partially explains the effect of cyanide as depression may be
srable or unstable depending on the. interaction of cyanide with the metai surface d e r
solvation of the coilector film. For example, the depression of iron sulphides is very stable
due to the formation of insoluble iron cyanide and hydroxide complexes at the minerai
surface. These complexes effectively prevent the adsorption of coiiector and hence
notation. Therefore whether readsorption does or does not take place with sulphide
minerals will depend on the relative nability of the cyanide sdts and complexes which can
be formed. For those cyanide sdts which are more stable than their corresponding
compiex ion, the consumption of fiee cyanide ion will only depend upon the surface area
of the minerai. Depression of minerais of this type will be continuous.
One of the most important aspects of cyanide in dotation is its extreme ability
to
dissolve the oxides, sulphides and xanthates of the transition metals. For exarnple, when
cyanide is added to a copper sulphide pulp, the following reactions may take place in the
solution (Wang 1989):
CU'-
+ 2CN tz C U C N ~ ~ , ~ ~
CuCN2,,,,
* CuCN,,,+ 1/2(CN)2(,,
CUCN,,,
+C N
Cu(CN)< + C N
Cu(CN)?
t,C U ( C N ) ~ ~
Cu(CN),= + C N tt Cu(CN);
CuzXz + 8 C N t, ~CU(CN)J'+ 2X
It is generaily accepted that at high concentrations of free cyanide ion, the equilibrium of
the stable complex Cu(CN)dm. Thus reaction (2.6.1.6) is used to represent the step-wise
dissociation of cuprous xanthate to fonn fkee xanthate ions and Cu(CN)dE. Considering
these concepts, it is reasonable to expect that the performance of selective flotation
systerns involving unstable depression, could be improved by preventing xanthate
readsorption.
Another important effect of cyanide is to reduce the redox potential of the flotation
pulp (Wang 1989). Cyanide is a strong reducing agent, stronger than sodium hydrogen
sulphide as a reducing agent. Furthemore, cyanide reacts with oxygen to form cyanogen
and/or cyanate:
2CN+H20+1/202+(CN)zg~+20K
(2.6.1.7)
(2.6.1.8)
( 0 9 2
(2.6.1.9)
(2.6.1.10)
On the other hand the effect of cyanide on the mineral surface is due to cyanide or
cyanide complexes which may be adsorbed on the minerai surface thus preventing the
adsorption of xanthate, the oxidation of the minera1 surface and xanthate to dixanthogen
(Wang 1989).
M[Cw/[HCN] = 4 . 7 1~O-''
(2.6.1.1 1)
can be calculated (Rogers 1976). Thus for each mineral at a given colector concentration
there is a cntical cyanide ion concentration above which flotation is not possible.
However, especidy in solutions of high pH value, the depressant action of the hydroxyl
ion must be considered. The depressive effect of cyanide further depends on its
concentration, the composition of the minerai to be separated, the pH cf the pulp, and
length of the xanthate hydrocarbon chain. The longer a heavy metai xanthate hydrogen
chain, the greater its stability in relation to cyanide. The use of sodium cyanide as a
depressant is restncted to alkali mediums as it hydrolyses in aqueous solutions forming
free alkali and hydrogen cyanide:
NaCN + H 2 0 ci KCN + NaOH
(2.6.1.12)
The presence of fiee alkali shifts the above equation to the left and eliminates the danger
of hydrogen cyanide evolution.
2.6.2
(2.6.2.1)
+ HS'
x IO-*; p K = 7.04
(2.6.2.3)
(2.6.2.4)
K2= M [ S = ] / [ H S 1
= 1.1 x
(2.6.2.5)
These equilibrium constants indicate that, on a molar basis, below pH 5 only 10 percent of
the H2S has ionized to
HS-.
At pH 7, half of the HShas ionized to HS-,
while between
pH 8 and 1 1 over 90 percent of the sulphide ions are HS-.At pH 12 the moles of HS(hydrosulphide) and S=are equal, while by pH 13, 90 percent of the ionization is to S'
(hydrogen sulphide). Therefore, hydrolysis and dissociation of sodium sulphide releases
HS- and S= ions into the solution and these can react with and modify the mineral surfaces.
To explain the mechanism of depression of sulphide minerais by the HS- ion, Leja
( 1 982) suggested that the presence of colIoidal sulphur on the mineral surface could be a
depressive factor, that thio anions and sulphanes may be formed on the mineral surface. or
that the hydrosulphide (HS-)
ion could destroy the collecter coating on the bulk floated
minerd.
Because hydrogen sulphide is a weak acid, prediction of minera1 depression by its ions
requires a knowledge of the system pH. The classic work elucidating this subject was
published by Sutherland and Wark (1955). They point out, based on contact angle data,
that, just as in the case of the cyanide ion, there is a critical hydrosulphide ion
concentration below which adsorption of xanthate is possible, and above which adsorption
is impossible.
2.6.3
sulphur-rich layer is fomed at the minera1 surface during oxidation, the mineral surface
may be hydrophobic. Evidently, the oxidized substances are hydrophilic and difficult to
Boat. But a high concentration of flotation reagents rnakes the seriously oxidized minerals
floatabie (Leja 1982). However, the minerals may be floatable to some extent even if they
are not too deeply oxidized. The mineral flotation depends mainly on the collector
concentration in the pulp and the oxidation extent of the minerals (Leja 1982).
Furthemore, if various conditions are properly controlled, oxidation depression may
become rather selective.
Potassium permanganate can be considered as an oxidizing agent. Rinelli et al. 1980
studied the reaction between xanthate and permanganate by infkared andysis of the
precipitate and its ethyl extract. The reaction was found to of be the redox type with
formation of dixanthogen and hydrated oxides of manganese. The different interactions of
xanthate and permanganate at various pH values can be ascribed to the different oxidizing
2MnOi + Hz0
t,2MnO
+ 20K + 5/202
pH 7:
Mn7-+3e t t M n 4 -
2MnOi + 20K o 2 ~ 1 1 0 4
+ ~Hz0
- + 1/202
Permanganate also exerts some action on the mineral surface. The permanganatemineral interaction can be explained in terms of its oxidizing power and the adsorption of
the Cree hydroxyls (reactions 2.6.3.2 and 2.6.3.4) on the surface of the sulphide minera1
(RineIli et al. 1980). Using infkared andysis the same authors showed that the overail
action of the permanganate on the surface of suiphide minerals was greatly augmented the
spontaneous oxidation phenornena that occur when sulphide minerals are exposed to air
and water.
to a koth phase (Fuerstenau et al. 1985). Whether or not bubble attachment and
aggregation occur is determined by the degree to which a particle surface is wetted by
water. When a solid surface shows littie affinty for water, the surface is said to be
hydrophobic, and the air bubble will attach to the surface. The stability of this attachent
is measured by the contact angle, 8, developed between the three phases: iiquid solid and
When the air bubble does not displace the aqueous phase, the contact angle is zero.
On the other hand, complete displacement of the water represents a contact angle of 180".
Values of contact angle between these two extremes provide an indication of the degree of
surface hydration, or, conversely, the hydrophobic character of the surface. Most minerals
are hydrophilic and, as such, must acquire their hydrophobic character by the adsorption
of surfactants, named collectors, in order for air bubble attachent to occur. The threephase equilibrium between the bubble, mineral surface, and water can be described by the
respective interfacial tensions according to Young's epuation:
YSG = :/SL
COS8
~ L G
(2.7.1)
where y s ~ y. ~ and
t YLG are the surface tensions at the soiid-Iiquid, soiid-gas, and liquid-gas
interfaces, respectively, and 8 is the contact angie.
This equation is usuaiiy combined with Dupre's equation. The fhe energy change per unit
area corresponding to the attachment process or work of adhesion between solid and
liquid (the displacement of the water by the air bubble) is referred to as Dupre's equation:
(2.7.2)
The free energy change c m then be expressed in t e n s of the contact angle by the YoungDupre equation: AG = y LG (Cos0 - 1)
(2.7.3)
For bubble adhesion to take place, AG c O in the liquid medium is concerned. Thus for any
solid-liquid system with 8 > O bubble adhesion is possible (Fuerstenau 1982).
A maximum contact angie is obtained when
~ S is
G
adsorption must take place with maximum effect at the solid-gas interface. However, in
practice, a minimum contact angle is required for notation to occur and this minimum
depends on the hydrated nature of the mineral and the solvent.
The free energy change for the bubble attachent process, AG, can also be described in
tems of the work of adhesion, WA, and the work of cohesion, WC, of water:
A G = W A - WC
(2.7.4)
For attachment to be effected, the work of adhesion of water must be less than the work
of cohesion of water, that is WA < WC.The work of adhesion is defined as the work
required to remove the liquid from the solid surface leaving an adsorbed water layer in
equilibrium with a saturated gas phase.
There are no strong wetting forces at clean nilphide minerai surfaces and the dserence
between WA and WCwill be smaii (Fiielstein et al. 1975). Any chernicd change at such
surfaces will tend to have an inordinate effect on the wetting characteristics, and the
surfaces will display indefite notation behaviour. Thus, hydrophobicity has to be
imparted to most of the minerais in order to float them.
Many attempts have been made to relate contact angle values to the floatability of a
sulphide systern the maximum contact angle is determined solely by the hydrocarbon
radical of the xanthate molecule. This is understandable as the mineral surface propenies
only designate the adsorption of the collector and hence establishment of contact. The air
bubble, however, is attached to the collector film and not the mineral surface. Therefore
the collector film controls the contact angle values. Contact angles have been s h o w to
depend also on surface potentials. Since dif5erent minerais adopt different surface
potentials in solutions of the same collector, some change in contact angle should be
expected on different minerals (Poling 1976). Although the contact angle is of great
importance, its accurate measurement is very difficult. The minera1 surface must be fresh
should enable direct identification of the adsorbed species on these surfaces. In addition,
the state of the adsorbent surfaces prior to and following a treatment in various adsorbate
solutions can be characterized by changes in the i&ared spectra. Most metal sulphides
have sufficient infkared transparency that spectra of the adsorbent with or without
adsorbed collector species can be recorded directly using either transmission or multiple
In the case of the transmission mode, the part of the radiation that travels through the
sample is detected. Absorption fiom the surfaces and the bulk is thus ascertained.
Therefore, to obtain information on the surface structure the surface/volume ratio must be
maximized. For t h i s reason, the techniques most comrnonly adopted, namely KBr pellets
and Nujol muil, utilize dry powdered solid samples (Marabini et al. 1993). It is not
possible to obtain in-situ meamrements since the absorption spectmm of the water present
in the solution would cover a good part of the anaipical range of the expenmental
spectrurn. Many studies on mineraVcollector-surface interaction have been performed exsitu. however, by comparing the untreated components and the treated compound. IR
transmission spectroscopy provides valid indications in the study of adsorption when a
chernical bond is formed between the minera1 and the collecter. In this case it is possible to
note major changes such as shifiing, and the formation andor disappearance of peaks in
the expenmental spectmm. The instruments generally used are dispersion spectrometers
that consist of a polychromatic radiation source. a monochromator and a detector.
However, more recently this type of apparatus has been superseded by interferometers
which have greater potential and ensure a considerable number of advantages. The most
signifiant advantages which exist in a Fourier Transform Idared (FTIR)interferorneter
compared with a dispersion spectrorneter are accuracy and repeatabiiity in waveiength
determination because of stability of the laser involved.
at 1 1 10 cm'' is reduced in htensity. Moreover, the metal xanhates, which have only one
C-S band also show bands in the region 800-950 cm-'. It should be rnentioned however
that there is disagreement conceniing the assignrnent of individual absorption bands in this
range (Little 1966). Nevertheless, these spectra illustrate that various xanthate compounds
may be readily identified by their absorption bands in the region 1250-1000 cm-'.
The term surface tension of a liquid, when used without qualification, refers to the
equilibnum surface tension in the boundary between the liquid and its vapour. The
simplest relation expressing the surface tension of binary mixtures (solutions) is an
additive rule;
y = yiX + y2(1-X),where y is the surface tension of a solution composed of X mole
Pure organic liquids of varying y, tested by Zisman on low energy solids gave linear
Cos8 versus ,y relationship with the intersection at CosB=l corresponding to yb
= y,,
where y, is the critical surface tension of the solid. The soiid characterized by a given y,
value is completely hydrophilic when immersed in liquids of yhcyc, and is hydrophobic
only in liquids of y,/,.
changes the surface tension of water oniy to a neghgible extent. An example of such
solutes are al@l xanthates. Other surfactants such as aicohols lower the surface tension of
their aqueous solutions more strongly than xanthates. Lately, Kelebek and Smith (1985)
correlated the value of the critical surface tension of wetting, with the cntical surface
tension of flotation, ycf, for difEerent minerais. The critical surface tension concept, when
applied in notation research, offers a unique way of testing the thennodynarnic flotation
cntenon. Two solids (A and B) characterized by dBerent values of y, can be selectiveiy
separated by flotation in alcohol solutions if the concentration of alcohol is such that
;/,
.A
<;/,,<yc!
This section describes those two minerais that were used in the present study, narnely,
enargite and chalcopyrite.
2.10.1
Enargite
Enargite, Cu3AsSa, is one of the temary phases in the system Cu-As-S sulphosalt as is
shown in Figure 2.10. la.
It has an orthorhombic crystal structure with each arsenic or copper atom being
surrounded by four sulphur atoms at the corners of a nearly reguiar tetrahedron, and each
sulphur atom being similady surrounded by a tetrahedron of one arsenic atom and three
copper atoms (Gajarn and Raghavan 1983). The As& groups are discrete and do not share
any sulphur atorns with one another. Specific gravity of enargite is 4.4 and consists of
48.42% Cu, 19.02% As and 32.56% S. The atomic anangement for enargite is s h o w in
Figure 2. IO.1b.
Red Mountain district, Quray and San Juan Cos; in Austria, at Matzenkopfl, Brixiegg
Tirol. From Bor, Yugodavia; in Italy, on Sardinia, at Alghero and Calabona; at Tsumeb,
Namibia; from Peru, exceptional crystds h m the Mina Luz Angelica at Quiruvilca and
aiso from Morocoha and Cerro de Pasco; in Argentina, in the Sierra de Farnatina, La Rioja
Province; in the Philippine Islands. at Mancayan, Luzon; and ffom the Chinkuashi mine,
Keelung, Taiwan (Anthony et al. 1990).
2.10.2
Chalcopyrite
Among the most common copper minerais, chalcopyrite, CuFeS2 is important in both
its distribution and its abundance in a great variety of ore deposits (Ramdohr 1980).
Figure 2.10.2a shows the composition of chdcopyrite in the Cu-Fe-S system.
bonded to two copper atoms and two iron atoms. Each copper atom and each iron atom is
tetrahedrally bonded to four sulphur atoms (Figure 2.10.2b). Its specific gravity is 4.3 and
consists of 34.5% Cu, 30.5% Fe and 35.0% S.
Chaicopyrite is a good conductor with a fairly narrow range of resistivity near 10"
ohm-m. Essentially all published determinations of semiconductor type are n-type. A gap
of about 0.6 eV is indicated by opticai absorption. It has not proven possible to determine
the gap independently by observation of intrinsic semiconduction because the donor
concentration is usually high, on the order of 10" cm", and because at high temperature
additional donors are produced by sulphur loss. The only published value of hole mobility
is 32 ~ r n ~ v - ~ (Shuey
s e c ' ~ 1975).
CHAPTER 3
Materiab, Equipment and Procedures
This chapter reviews the techniques and rnethods that were ernployed to study the
surface properties and flotation phenornena of enargite and chalcopyrite. Synthetic
enargite Swas the major sample used in this study. Natural enargite and chalcopyrite
samples were also selected to compare with the synthetic enargite.
The minerai was prepared and midied in two foms: as a massive sample with a polished
surface for use as an electrode or for contact angle meanirement, and, as fine particles for
adsorption and flotation tests, etc. Methods for preparing and polishing a massive surface
were standardized for ensuring the surfkce was free of contaminants such as organic
Synthetic enargite was prepared by mixing very pure copper, arsenic and sulphur
powders in the stoichiornetric ratio in a Pyrex capsule. A vacuum of 10" mm-Hg was then
drawn for 24 hours by a Duo Seal mode1 1402 vacuum pump and then the capsule was
seded. The capsule was heated to 500C in a Sigma Type K h a c e capable of 0- 1370 O
equipped with a thermocouple, and held at this temperature for 17 days until the reaction
was complete. Evacuation was done in order to prevent oxidation of elements in the tube
and to produce an inert atrnosphere for reactions. The prepared synthetic enargite sample
was ground in an agate rnortar to -200 mesh. The -325 mesh size fraction was used for
adsorption tests and the size fraction of -200+325 mesh was used for flotation tests. This
fiaction is neither too fine to be carried away by agitation nor too coarse to escape lifting
by the gas bubbles. The massive sample was selected for optical, rest potential and contact
ande studies. The purity of the synthetic enargite sample was verified by a Rigaku
Rotaflex mode1 RU-2OOB Rotary Anode X-ray DitFranometer to be greater than 99%
enargite. The peaks obtained in the x-ray deaction pattern are summarized in Table 3 . 1
and shown in Figure Al in Appendix Al. The polished surfaces of synthetic enargite were
prepared for rnineralogical identification. Chernical analysis of the sample was also
determined for copper, arsenic and sulphur.
Table 3.1: X-ray powder diffraction data for synthetic enargite compared to some indexed enargite.
Reference
Strongest Lines
Svnthetic enargite
3.21/% 1.86/9. 2.84/8. 1.7318. 1.59/5
Synthetic enargite by Maske and Skinner ( 1977) 3.206k L1.8S/9,2.83 9/8. 1.728/8. 1. %6/5
3.2Un 1.86/9. 2.87% 1.73/6.1.59/5
Natural enargite from Quray (Maske and
Skinner 1977)
The natural enargite used was Yom Butte, Montana and supplied by Ward's Natural
Science Establishment Inc. It was crushed to minus 5 m size and hand-sorted. The
purest particles were selected for grinding in an agate mortar and sieved into two size
fractions. The individual size fractions were stored in air-tight glass bottles and then
stored in a vacuum desiccator to prevent oxidation. The naturally occumng enargite
mineral grains were very fine and always closely associated with pyrite. A polished surface
of natural enargite was also prepared for mineralogical examination. Naniral enargite
almost invariably contains several percentages of Sb substituting for As. The slight
differences between the x-ray diffiaction properties of synthetic and natural enargite are
almon certainly due to the ceil edge changes consequent on this substitution (Maske and
Skinner 1977). Opticai properties are apparently liale affected by the substitution of small
arnounts of Sb for As.
A polished thin section of synthetic enargite was studied and cornpared with the
natural sample thin section. The synthetic enargite was characterized by spongy habit.
Crystals occurred as anhedral to subhedral grains. They showed light bluish grey to
pinkish brown colours. The natural sample seemed a little darker. Both samples showed
strong bluish-brownish anisotropy and weak pinkish grey to violet paleochroism. Deep red
internal reflectance was rarely observed. Enargite was associated with pyrite in the natural
The chalcopyrite sample from Durango, Mexico was supplied by Ward's Natural
Science Establishment Inc. It was aiso crushed to minus 5 mm size, harici-sorted and the
purest particles were ground in an agate mortar, screened into two size fiactions and then
stored in air-tight glass containers and a desiccator. The chemical and rnineralogicai
analyses of the prepared sample reveaied a very pure chalcopyrite sample.
The chernical analyses of samples were deterxnined by a Perkin-Elmer model 2380
Atomic Adsorption Spectrophotometer and a LEC0 model SC-444DR Carbon and Dual
Range Sulphur Andyzer. Ln order to eliminate the effect of particle size on adsorption
density the surface area of each sample was determined. The specfic surface area was
evaluated with a Quantasorb Surface Area Analyzer, using nitrogen gas adsorption and
applying the BET isotherm. Tables 3.2, 3.3 and 3.4 show the chernical and mineraiogical
analyses. the surface area and the size distribution of samples, respectively.
Table 3.2: Chemical and mineralogical analyses of synthetic enargite. natural enargite and
chalcopyrite.
Chemical M y s i s . %
Cu
Fe
As
S
Mineralogical Analysis. %
Enargite
Pyrite
Other
Chaicopyrite
Naniral Enargite
38.6
8.7
15.1
36.5
79.8
18.8
1.4
Chalcopyrite
33.2
29.9
1
I
Synthetic Enargite
48.42
35.6
19.02
32.56
100
2.6
1.2
96.2
Infiared spectra for the synthetic enargite without, and contacted with potassium amyl
xanthate were detennined with a BOMEM Michelson Series Infiared Spectrophotometer.
In the preparation of the electrode for the electrochemical study, a copper wire was
attached to one end of the rnineral by means of SPI Silver Epoxy cernent. Before
cementing the copper wire to the surface, the specimen was rough ground in order to
make the contact resistance as low as possible. The copper wire was threaded through a
length of glass tubing and the rnineral and adjacent 1 cm of tubing embedded in mounting
epoxy. M e r curing, the lower face of the mineral was exposed by grinding away the
epoxy. The electrode surface was prepared on successiveiy finer grades of silic~ncarbide
paper. The minera1 surface was refreshed between each electrochemical experiment by
grinding on 600 grade paper. Potentials were measured with a CMS 105 DC Corrosion
Measurement System and a digital rnultimeter model Omegameter H H M 5 7 4 a sanirated
calomel electrode being used as reference.
TabIe 3.3: Spectfic surface ara of synthetic enargile. natural enargite and chalcoprite.
Particle Size
-325
-200+325
Synthetic Enargite
0.499 1
0.245 1
Nafurai Enargite
0.7225
chalcopyite
0.6496
0.3153
O. 1664
Potassium Amy1 Xanthate (PAX), which is the mosi commonly used collecter for the
flotation of copper minerals, was used in this study. Reagent grade potassium amyl
xanthate, frorn Cyanamid, was purified by recrystallization fiom acetone and precipitation
with diethyl ether (Pang 1991), then vacuum dried and stored under vacuum (Appendix
A6). The potassium amyl xanthate concentration was determined by a Perkin-Elmer
a Fisher Scientific model Accumet pH Meter: this value is within the range of industrial
practice. Sorne tests were conducted at other pH values to investigate the effect of pH on
Table 3.4: Particle size distribution of synthetic enargite. natrual enargite and chalcopyrite.
Particle Size
(Meshl
-200+325
ri
-325
Size Fraction
-74+53 (m)-200+270 (Mah)
- 5 3 4 4 " -270+325 "
1 4+37
"
-325+400 "
Synthetic
Enargite
61.6%
38.40/0
100%
20.7%
Natumi
Enargite
60.5%
39.5%
100%
31.8%
Chaicopyrite
--
62.6%
37.4%
-
100%
24.2%
3.2 Procedures
3.2.1
Adsorption
The agitation method was used for determining the adsorption density of collector on
the rnineral surface. 0.5 g of finely ground rnineral (-325 mesh) was introduced into a 50
The desorption of the collecter &om the synthetic enargite surface by pure water was aiso
investigated. The technique used is described below. At the end of the adsorption test a
known volume of solution was removed and replaced by water, adjusted to pH 9, agitated
for set tirne intervals of one hour and the equilibrium xanthate concentration was
measured.
Two types of tests were conducted for the depressant effect. In the first series of tests
the minera1 was pre-conditioned in the xanthate solution to deterinine the effect of
depressant on pre-adsorbed xanthate. In the second series, the minerai was conditioned
with depressant prior to the xanthate addition. The results would demonstrate that the
depression action is by either preventing xanthate adsorption or desorbing it frorn the
surtace.
The effects of sodium cyanide, sodium sulphide and potassium permanganate on preadsorbed xanthate were evaluated by removing 2 ml of the solution f i e r the xanthate had
reached equilibriurn. Then 2 ml of depressant solution with sufficient strength was added
to give the required concentration in the tube. The sample was centrifuged for 30 seconds
prior to the solution removal to prevent any mineral loss. In the presence of depressant.
agitation was resumed for set time intervals, after which the sample was centrifuged for 30
seconds to prevent further reaction. The xanthate concentration was then determined.
The effects of sodium cyanide, sodium sulphide, potassium permanganate and copper
sulphate on adsorption were evaluated by 10 minutes agitation of samples in their
respective solutions at the required concentrations. The samples were then washed with
distilled water three times to eliminate residuai ions in suspension. Adsorption tests were
t hen performed.
To evaiuate the effect of oxidation on the adsorption density of xanthate, the minerai
sample was placed in the adsorption tube and 25 ml of distilled water was added. Then air
was bubbled below the water surface at a flow rate of 300 mVmin. M e r 20 minutes
distilled water was replaced by the collector solution, conditioned for one hour and then
the adsorption density was detemiined.
AU adsorption tests were performed cwice and the average is reported as the
3.2.2 Flotation
The sarnple was conditioned for 20 minutes with a collector solution in a micro
flotation cell. Flotation was conducted using a 0.5 g mineral sample of -2001-325 mesh in a
modified Hallimond tube with an effective volume of 50 ml which consists of a flotation
column and a chamber at the top for collecting the concentrate. It was operated at a
constant nitrogen flow rate of 40 d r n i n through a fritted glass disc sealed in the bottom
of the column. This amount of gas is sufficient to ensure complete flotation of a tloatable
materiai. Nitrogen gas, used as the carrier gas in the flotation tests, might prevent any
effects fiom the oxygen contained in the atmospheric air. As mot flotation occurred
immediately after the introduction of gas into the cell, the flotation tirne was limited to one
minute for obtaining reproducible results. Agitation in the ce11 was provided by a micromagnetic stirrer. The flotation products were filtered, dried and weighed.
For studying the effects of sodium cyanide and sodium sulphide on pre-adsorbed
xanthate, the rnineral was conditioned with PAX for 20 minutes and then with depressant
for dierent tirne intervals foilowed by one minute of flotation. The effect of K M n a on
pre-adsorbed xanthate was evaluated after 10 minutes contact with the different
permanganate concentrations.
In another series of tests, a sufficient amount of depressant, or copper sulphate. was
added to 25 ml of distilled water to give the required concentration and the pH was then
adjusted. The mineral and depressant, or copper sulphate, were conditioned for 10
minutes. Then, 25 ml of 40 mg/l potassium amyl xanthate solution was added to give 20
mg/l PAX concentration in the ceii and conditioned for 20 additional minutes. Fiotation
then followed.
To investigate the effect of oxidation, the flotation tests were carried out as a function
of aeration tirne. Air was initially bubbled at a flow rate of 300 d m i n in distilled water
along with mineral. Afler specific time intervals. distilled water was replaced by collecter
solution, conditioned for 20 minutes and then floated for one minute in the cell.
The effect of pulp potentiais on the floatability of the mineral was investigated by
using an electrode pair consisting of an indicator electrode and a reference electrode in a
rnicroflotation-electrochernical cell. This cet1 was similar to the modified Hallimond tube
used in the flotation tests. It comprised a reference eIectrode cornpartment and a mineral
electrode cornpartment, which were comected by means of glas tubing c o ~ e c t e dto the
ce11 cornpartment. The ce11 was first loaded with rnineral and then filled with PAX solution
conditioning was perfonned by applying the redox ragent using a syringe pump and the
potentiai measurement was carried out after 10 minutes. The flotation test was then
carried out.
Sodium sulphide and potassium permanganate were used to control the pulp potentiais. A
minerd electrode was used as an S c a t o r electrode and potentials were measured against
a sanirated calomel reference electrode (SCE).
Ail flotation tests were duplicated and the average is reported as flotation results.
A hand picked enargite sample was used for the contact angle study. The bubble
attachent method was used for the contact angle measurement. In this technique a
bubble reieased below the specimen rises through the liquid and contacts the minerai. If
the mineral is gas-avid the bubble adheres, developing a finite contact angle. The mineral
specimen is suspended in the test solution by a holder, and adjustment is easily made by
turning and sliding the specimen holder to the desired position with respect to the optical
pans, light path, and the picture frame. The sample was polished under distilled water
prior to each test to make a fresh surface and a contact time of haK hour was taken as
sufficient tirne for equilibnum between PAX and enargite. M e r equilibnum an air bubble
was brought into contact with theenargite surface and 10 minutes later the contact angle
was measured. To minimize the effect of hysteresis, several readings were taken at various
spots the mineral s d a c e and the average of these readings was taken as the tnie contact
angie.
The effect of sodium cyanide on the contact angle was studied by adding the desired
amount of sodium cyanide to the cell after equilibrium had been attained between the
xanthate and enargite. The air bubble was placed on the mineral surface withm 3 minutes
of the sodium cyanide introduction, and the contact angle was measured 10 minutes later.
3.2.4
For the infrared absorption study, 2 grarns of -325 mesh synthetic enargite were
ground in a mortar for two hours. The sample was then added to a solution containing the
desired amount of PAX. The pH was adjusted to the required value and the system was
conditioned for 20 minutes. M e r conditioning, the enargite sample was centrifuged, dried
at room temperature and mixed with Nujol oil to provide the mull for infiared analysis.
3.2.5
Mineral Solubility
The solubility of synthetic enargite was determined by contacting one gram of -325
rnesh mineral with 20 mi of distilied water (pH 5.3). The solution was set at pH 5.3 to
prevent precipitation of copper or arsenic hydroxides. The water-mineral mixture was
then rolled for 30 minutes and filtered on a 0.1 pm Micropore filter. The copper and
arsenic content of the filtered solution were determined.
To investigate the extent of oxidation, a test was carried out by placing one gram of
-325 mesh enargite in a 150 ml beaker with 100 ml of distilled water and aerated with air
at a fiow rate of 200 rnlhin. Agitation was provided by a magnetic tirrer. M e r aeration
for a given tirne period, the solution was filtered and the filtrate was analyzed for copper
and arsenic.
a magnetic stirrer. One nomal hydrochlonc acid was then added gradually in smali
arnounts and the pH of the solution was measured each time &er the addition of acid. The
volume of acid used was recorded. The cumulative acid addition was ploaed versus pH.
This procedure was repeated once for a biank electrolyte solution and the interception
point of the two curves was taken as the zero point of charge.
was determined. The same measwement was also conducted in distilIed water. A test was
aiso performed using ethyl xanthate under the same conditions.
CHAPTER 4
Flotation Chemistry of Synthetic Enargite
4.1 Results
41.1
Adsorption
A prelinary shidy of adsorption kinetics for four levels of xanthate concentration
showed that equilibrium was reached d e r about 10 minutes agitation for 10 and 15 m g
plateau within 60 minutes for higher xanthate concentrations as s h o w in Figure 4.1. la.
.....................
...............
+Initial P A X
Conc.= 15 mg;l
PAX
Conc.=SO mg11
-.t- Initial
..
Adsorption T i m e ( m i n u t e s )
Figure 4.1. la: The adsorption of potassium amyl mthate on synthetic enargite as a
function of time at pH 9.
The xanthate adsorption was most rapid in the initiai 10 minutes. Al1 the following
adsorption tests with synthetic enargite were thus performed for one hour.
+Adsorption
iaothtrm
-C- D e s o r p t i o n isothcrm
0.1
:
0.1
, , ,
10
IO0
Figure 4.1.1 b: Adsorption and desorption isotherms for PAX on synthetic enargite at pH 9.
The isotherm cuve exhibits three different regions. At low equilibrium xanthate
concentrations (less than 1.22 mgA), the density of xanthate on synthetic enargite increases
rapidly according to the Freunlich adsorption equation which can be represented by:
T=k(C)
(4.1.1.1)
where:
The second part of the curve, a plateau region where the adsorbed species remains
relatively constant, gives a Langmuir type plot. Finaliy further adsorption takes place
(above a concentration of about 28.75 mg/l) at a lower increase per unit change in
concentration.
-4ccording to the Freundlich adsorption equation a straight line should be obtained in
a log-log plot. The result of Figure 4.1.1 b shows a straight line relationship up to 1.22
m g equilibrium xanthate concentration and then there is a discontinuity which indicates a
change in the surface characteristics of the mineral as a result of the adsorption of several
layers of collecter.
r=(~crj(
I +qc)
(4.1.1.2)
where:
and q is a constant. It was tested by plotting C i against C. The values of C and r were
those correspondhg to pH 9 in Figure 4.1. lb. This plot should give a straight line if the
Langmuir equation was vaiid. Figure 4.1. lc shows that C K appears to be lineariy related
to C for equilibriurn xanthate concentrations from 1-22mg/i to 28.75 mgn. The testing of
the Langmuir equation is not sensitive enough for higher surface coverage.
10
20
30
40
50
60
70
80
Figure 4.1. lc: Langmuir plot of C K versus C for the adsorption of xanthate
on synthetic enargite.
as 25A2 (Gaudin et al. 1956), the amount of xanthate required for a monolayer coverage
was caiculated (Appendix A4) to be 0.671 mg/g (1-344 mg/m2). The shifting of the
isotherm plateau in Figure 4.1.lb to a higher adsorption density indicates vertical
monolayering or a combination of vertical and flat orientations, instead of lying totally fiat
on the surface (Cheng et al. 1994). This also indicates physicai adsorption of additional
layers of xanthate on the mineral surface.
From the isothem curve (Figure 4.1.1b) it can be seen that at very Iow initial xanthate
concentrations (5 mg/l) the amount adsorbed is below the calculated monolayer. With
increase in initial xanthate concentration the amount of xanthate absorbed is greater than
that calculated for a monolayer on the bais of the cross-sectionai area of the xanthate
radical. The results of the desorption tests (Figure 4.1.1b) show that no rneasurable
desorption could be obtained with pure water.
The surface area for the flotation fraction (-200+325 mesh) was also measured in
order to relate the amount of collector adsorbed. The result of adsorption density for this
size fraction shows that the adsorption density is very close to that obtained for the -325
mesh fraction. However, because of the lower surface area the equilibrium xanthate
concentration increased due to the fewer available sites for xanthate adsorption (Table
4.1.1 S b in Appendix Ag).
4.1.1.1
Experiments were conducted to study the effect of sodium cyanide on the preadsorbed xanthate at pH 9. The xanthate solution concentration was kept constant at 20
mg/l. Figure 4.1.1.1 shows that an increase in the concentration of sodium cyanide would
cause the desorption of PAX eom the synthetic enargite surface. As the cyanide contact
time increases, a rapid desorption of xanthate nom the synthetic enargite surface occurs.
At 15 mgh sodium cyanide, a maximum of 93 -5 percent of xanthate is removed within 60
seconds. M e r 120 seconds a slight re-adsorption takes place and the adsorption density
recovers to 27.6 percent of its original value within 20 minutes. k the lower cyanide
concentrations, readsorption of xanthate commences afler about 180 seconds and never
recovers to its original value.
The effect of sodium cyanide on the xanthate adsorption was evaiuated by first
conditioning the synthetic enargite sample in sodium cyanide solution and then performing
adsorption tests. At 20 mgA xanthate concentration the adsorption density is 0.894 mplm'
which is 22.4 percent of the adsorption density without the NaCN addition. The results
are given in Table 4.1.
These results show that the effect of sodium cyanide addition pior to the xanthate
adsorption is lower than the effea of cyanide addition on the pre-adsorbed xanthate on the
minerai surface.
Table 4.1: The effect of depressants on the .xanthate adsorption on synthetic enargite.
1
Original
3.99 1
Test Conditions
Initial PAX Conc.=LO.O ma, Conditioning Tirne= 10 min.. pH=9.0
Adsorption Densiv mglm'
Fim Conditioned With Depressant
Aeration, 20 min.
NaCN. 15 mgil Na2S. 10 mg/i
KMn04,50 mg/
2.395
2.275
2.7 16
0.894
S o d i u m C y a n i d e C o n t a c t Tirne ( m i n u t e s )
Figure 4.1.1.1 : The effect of sodium cyanide concentration and contact tirne on the
pre-adsorbed .white on synthetic enargite at pH 9 and 20 mg/i
initial PAX concentration.
41.1.2
The effect of sodium sulphide concentration and contact time on the pre-adsorbed
xanthate is presented in Figure 4.1.1.2. The results show that with an increase in sodium
sulphide contact time there is an increase in desorption of xanthate Eom the synthetic
enargite surface. The desorption of xanthate is very fast in the first five minutes and at 10
These results show a small rate of desorption after 5 minutes contact with sodium
sulphide.
The effect of sodium sulphicie on the xanthate adsorption density, conducted by
conditioning the mineral sarnple with sodium sulphide followed by the xanthate addition, is
given in Table 4.1. The results indicate that the xanthate adsorption is 68 percent of the
by xanthate addition has a lower effect on the reduction of xanthate adsorption than on the
S o d i u m S u l p h i d c C o n tact Tim
(m i n u t e s )
Figure 4.1.1.2: The effect of sodium d p h i d e concentration and contact time on the
pre-adsorbed .suhate on synthetic enargite at pH 9 and 20 mg/i
initial P A X concentration.
4.1.1.3
K m 4
stops &er 120 seconds but at 25 mg/l, readsorption continues to 5 minutes with a very
small increase after that. For 50 mg/l KMnOd concentration there is a readsorption of 27.7
percent of the original value at 20 minutes of contact tirne.
.-
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.
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10
15
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Ah
. . . ............
.
.
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20
K M n O 4 Contact T i m c ( m i n u t e s )
Figure 4.1.1.3: The &ect of KMnOd concentration and contact time on the
pre-adsorbed .uanthate on synthetic enargite at pH 9 and 20
mg/l initial .uanthate concentration.
Table 4.1 gives the effect of KMn4 on the adsorption density of PAX on synthetic
enargite by pre-conditionhg the mineral sample with KMnOJ followed by xanthate
addition. The adsorption density is reduced ater conditioning the synthetic enargite with
on the pre-adsorbed xanthate on the minera1 surface than on the reverse reagent addition
sequence.
4.1. t .4
0.1
1O
1O0
Figure 4.I.1.4:The effect of copper sulphate concentration on the adsorption density of PAX
on synthetic enargite at pH 9.
4.1.1.5
Efiect of pH on Adsorption
Figure 4.1.1.5a represents the adsorption isotherms for synthetic enargite at three
different pH values. The adsorption curve for pH 1 1 is displaced in the direction of lower
adsorption and higher equilibrium xanthate concentrations with respect to the curves for
pH 7 and pH 9. This indicates a decrease in adsorption density at high pH regions.
0.1
1O
100
E q u i l i b r i u m X a n t h a t e C o n c e n t r a t i o n (rn g t l )
Figure 4.1.1 Sa: Equilibrium adsorption of PtV( on synthetic enargite at dinerent pH values.
of pH when the initial concentration of the colIector is kept constant. The reiationship
between pH and the adsorption density of xanthate is presented in Figure 4.1.1 S b . The
results show that above pH 9 the adsorption density decreases with increasing pH for
xanthate concentrations of 20 and 50 rng/l. Below pH 9 the adsorption density remains
relatively constant. At 10 mg/l xanthate concentration there is no change in adsorption
density to pH 1 1 but decreases with change to pH 12.
-C- P A X C o n c . = 10 m g / ]
I. P A X C o n c . = 2 0 mg11
PAX Conc.=50
mg/[
Figure 4.1.1 .W: The e f k t of pH on the adsorption density of PAX on synthetic enargite.
The effect of aeration on the xanthate adsorption was evaluated by the aeration of
synthetic enargite fotlowed by adding xanthate. The result is given in Table 4.1. M e r 20
minutes aeration, the adsorption density is 2.395 mg/m2 which is 60 percent of the original
adsorption density.
41.2 Fiotation
Figure 4.1.2 shows the relationship between the coiiector concentration and the
flotation recovery of synthebc enargite at pH 9. This relationship tends to be a parabolic
one with a higher increase at low concentrations and a graduai asyrnptotic approach at
higher values of xanthate concentrations. The recovery increases to about 75 percent at 20
mgIl PAX and to a plateau at an approximately maximum recovery of 78 percent at a
O riginal X a n c h a t e C o n c e n t r a t i o n (rn g . 1 1
Figure 4.1.2: Fioatability of synthetic enargite using potassium amyl .xanthate and
potassium ethyl .uanthate.
collecter concentration of 20 mgll. Above 20 mg/l xanthate concentration aimoa the sarne
recovery is obtained with both amyl and ethyl xanthate.
4.1.2.1
sodium cyanide concentration. The results show that the recovery decreases to 43 percent
with 5 m g sodium cyanide at 2 minutes contact tirne. The synthetic enargite depression is
increased at the
effectiveness after prolonged retention time. As the retention time extends to 20 minutes. a
10-1 5 percent increase in the synthetic enargite flotation recovery is obtained.
10
15
20
Figure 4.1.2. la: The effect of sodium cyanide concentration and contact time on the tloatabilih
of synthetic enargite at pH 9 and 20 mg/i PAX concenuation.
The synthetic enargite surface was conditioned for 10 minutes in a 15 mg11 sodium
cyanide solution followed by the xanthate addition and flotation. The flotation recovery of
Test Conditions
Initiai PAX Conc.=2O.O mgi. Conditionkg Tirne= 10 min.. pH=9.0
1 Original 1
71.95
NaCN, 15 mgR
21.00
55.60
45.08
- - - -
1
1
1
Aeration. 20 min,
50.25
Figure 4.1.2.1 b shows the eEect of xanthate concentration on the synthetic enargite
flotation in a 15 mgIl sodium cyanide solution. The increase in xanthate concentration
improves the synthetic enargite recovery but retards the rate of maximum depression to 5
minutes and the recovery decreases to about a maximum of 34 percent at 20 minutes
contact time.
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-..-*.-.----.-.-.--..--.----.
.
.. .. .. . .. .. .. ..
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.
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. . . .
P A X Conc.=20 m g / l
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.. ................-......,...*....-.............**..-.*...............+.--...-.....
... ... .. .. .. .. .. .. . .. .. .. . . . .
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-..--.-...--....-.-..--..~.-~--..-..---.-*~~.---...*
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Figure 1.1.2. Ib: The effect of sodium cyanide contact time and .uanthate concentration on the
floatability of synthetic enargite at pH 9 and 15 mg/l sodium cyanide
concentration.
Decrease in particle size or increase in surface area at constant xanthate and sodium
cyanide concentrations aiso improved the recovery as s h o w in Figure 4.1.2. l c, but both
particle sizes recovered to the same final recovery of about 24 percent within 20 minutes.
10
15
Figure 4.1.2. Lc: The effect of sodium cyanide contact time and panicle sire on the
Boatability of synthetic enargite at pH 9. PAX concentration of 20
mgli and 15 mg/i cyanide concentration.
recovery is presented in Figure 4.1.2.2. The results show that the depression of synthetic
enarsjte increases with the sodium sulphide contact time. At initial 5 minutes contact, the
enargite flotation recovery decreased rapidly fiom 75 percent to 64.23, 52.28 and 45.74
percent and then to 63.99, 48.95 and 41 -96 percent after 20 minutes for sodium sulphide
.
.
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.
..
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.__._...__..._.
-+
.. - Sodium Suiphidc C o n c . = 5 m g / [
.
.
. ........_..
.
. _. _ _ _
-.
..
..
.
.
.
+S o d i u m S u l p h i d c C o n c . = 10 m g l l
.
.
.
.
.
.
+S o d i u m S u l p h i d c C o n c . = 1 5 m g i l
.
.
.
.
.
.
1O
15
-..*
20
S o d i u m S u i p h i d e C o n t a c t Tirne ( m i n u t e s )
Figure 4.1.2.2: The effm of sodium suiphide concentration and contact time on the fioatability
of synthetic enargite at pH 9 and 20 mgll PAX concentration.
for 10 minutes conditioning with sodium sulphide. The result is shown in Table 4.2.
Figure 4.1.2.3a shows that a neutral solution to pH 1 1 has little effect on the
Figure 4.1 -2.3a: The effect of flotation pH and pH regdators on the floatability of
synthetic enargite at 20 mg/l PAX concentration .
5-33 percent fiom pH 6 to pH 1 1, but at pH 12 the flotation recovery is very close for both
xanthate concentrations.
4.1.2.4
Figure 4.1.2.4a shows the results of flotation tests with potassium permanganate as an
oxidant on the depression of synthetic enargite pre-adsorbed with xanthate. Results show
that synthetic enargite is depressed by increasing the concentration of KMn04. The
concentration of potassium amyl xanthate was maintained at 20 mg/l throughout all tests.
K M no4 Concentration
mg11
The results obtained by conditioning the synthetic enargite sarnple in 50 mgA rCMnO
solution followed by xanthate addition and notation are presented in Table 4.2. The results
show that 45.08 percent notation recovery was attained. A stronger depression effect on
the synthetic enargite notation was obtained with the effect of KMIIOJ on the preadsorbed xanthate.
The combined effed of KMnO, concentration and solution pH on the synthetic
4.1.2.5
The effect of cupric ions on the synthetic enargite flotation may be seen from Figure
4.1.2.5. The flotation tests were conducted with various quantities of copper sulphate at
pH 9 using a collecter concentration of 20 mg/l. The results indicate that the addition of
copper sulphate increases the flotation recovery fiom 75 percent to about 87 percent at a
1O
iO0
C o p p e r Sulphatc Concentration ( m g / l )
4.1.2.6
Figure 4.1.2.6 shows that aeration decreases the recovery of synthetic enargite.
Under the test conditions, 20 mgA PAX and pH 9, the recovery decreased from 75 percent
to 30 percent afler aeration for 1 hoor.
A eration T i m c ( m i n u tes)
4.1.2.7
enargite, notation tests were performed at pH 9 with 20 mgn PAX. Sodium sulphide and
potassium permanganate were used as redox reagents to control the pulp potentials. The
results are shown in Figure 4.1.2.7.
100
200
Figure 4.1.2.7: Relationship between flotation recovery and pulp potentiai for synthetic
enargite at pH 9 and 20
PAX concentration.
ma
The anodic Iirnits were controlled by adding potassium permanganate, while the
cathodic lirnits were controlled by adding sodium sulphide. Potential measurements were
carried out 10 minutes after introduction of redox reagents. Synthetic enargite floated weil
in -3 10 to -58 (mV vs. SCE) potential ranges. The floatability was poor in either more
oxidizing or more reducing potential ranges. Between -500 and -350 (mV vs. SCE), the
recovery was less than 50 percent. When Eh was raised to high positive values, flotation
was also suppressed.
4.1.3
Adsorption-Flotation Relationship
concentration. Above this point, the synthetic enargite recovely increases only 3 percent
although the initial xanthate concentration is increased to 30 mg/l. The xanthate
adsorption density increased to 4.5 and 4.6 mg/m2 at initial xanthate concentrations of 30
and 50 mgil, respectively.
A d s o r p t i o n Denrity (rng:m2)
The effea of xanthate concentration and pH on the synthetic enargite contact angle
was investigated. Figure 4.1.4a shows that the contact angle increased with xanthate
concentration up to 77A0 at a concentration of 20 mg/l. Mer that there was a srnail
increase in contact angle to a maximum of 80.4' at 50 mg/l PAX xanthate concentration.
The plateau observed in this graph is started at about 20 mgIl xanthate concentration
which is in good agreement with the adsorption-dotation relationship curve. At high
alkaline regions a decrease in contact angle is observed. The dserence is less than 5" at
10
20
30
40
50
Figure 4.1.4a: The effct of .xanthate concentration and pH on the contact angle of synthetic
enargite.
The effen of pH on the contact angle is also presented in Figure 4.1.4b.Results show
a decrease in contact angle as the pH is above 9. The pH of the solution had no major
effect on the contact angle for al1 concentrations of xanthate at pH 6 to pH 9.
1,
P.4X C o n ~ . I=O mgil
PH
Figure 5.1.4b: The effect of pH on the contact angle of synthetic enargite.
The effect of sodium cyanide on the contact angle of synthetic enargite can be seen in
Figure 4.1.4~. Synthetic enargite was conditioned with xanthate followed by NaCN
addition. With increasing NaCN concentration the contact angle decreased to below 20" at
a cyanide concentration of 15 mg/l. The most effective depression began at 5 m g NaCN.
The results were obtained by conditioning with sodium cyanide for 3 minutes.
0.1
1O
100
4.1.5
Inf?ared spema were obtained for synthetic enargite before and d e r contact with
amyl xanthate at pH 7 and 30 mgn PAX concentration. At this xanthate concentration the
amount of adsorbed xanthate is above the calculated monolayer. These spectra are
presented in Figure 4.1.S. Four principal xanthate absorption bands appear at 1260. 1205.
1030 and 875 cm" .
Figure 41.5: lnfrared spectra of synthetic enargite in the presence (Curve A) and
absence (Curve B) of potassium amyl santhate.
The solubility of synthetic enargite was determined by contacting one gram of -325
mesh mineral with water for 30 minutes and then the copper and the arsenic contents of
the solution were determined. The results for the solubility of synthetic enargite are shown
in Table 4.3. The results show that the copper and arsenic concentrations were 4.1 and 3.9
mgfl, respectively. The investigation for the extent of oxidation was also carried out. The
results are also presented in Table 4.3. The concentration of copper and arsenic increased
for aeration intervals up to 60 minutes. However their concentrations decreased d e r
aeration for 120 minutes. The concentration of arsenic was always higher than that of
copper.
Table 4.3 : Solubility of synthetic enargite at pH 5.3.
Weight (g)
Cu (m@)
As (md)
The zero point-of-charge (zpc) of synthetic enargite was determined using the
adsorption of potential determining ions technique described in section 3 - 2 6 . The
relationship between pH and the amount of acid for a blank electrolyte solution and a
solution containing synthetic enargite is presented in Figure 4.1 -7. The interception point
of the two curves represents the zero point of charge. The zpc value for synthetic enargite
Figure 4.1.7: Detennination of zero point of charge of synthetic enargite using the
adsorption of potential determinhg ions technique.
The results of rest potential studies for synthetic enargite &er 10 minutes show that
the rest potentials in a 6 . 2 5 ~ 1 M
0 ~solution of potassium amyl xanthate and distilled water
are -0.1 10 V and +0.080 V vs. SHE, respectively. The equilibrium potential of a
dixanthogedxanthate couple for 6 . 2 5 ~ 1 0M~ potassium amyl xanthate
CE" = -0.159 V)
was calculated fiom the following formula (Hepel and Pomianowski 1977) to be 0.030 V:
E = Eo - 0.0591 1 0 g M
(4.1.8.1)
The rest potential in the sarne concentration but for ethyl xanthate was also determined to
be -0.020 V vs.
(EO= -0.060 V) was calculated to be 0.130 V vs. SHE. There was a dinerence of 90 m V
4.2 Discussion
4.2.1
Adsorption
rate of diaision through the product layer. If the adsorption coating on the mineral
surface is very smaii (fiactions of a monolayer) the adsorption rate may be govemed
prirnarily either by the rate of diffusion through the tiquid layer surrounding the solid
surface or by the reaction rate, depending on which of these processes is the slower
(Bogdanov et ai. 1960). The ion exchange theos, seems to be the rnost satisfactory
expianation for adsorption of xanthate on sulphide rninerals. This theory assumes that
xanthates adsorb on sulphide surfaces by exchange with adsorbed ions, such as carbonate,
hydroxyl and sulphur oxyion (Fuerstenau et al. 1971). Using X-ray Photoelectron
Spectroscopy (XPS) and Infked (IR) refiection spectroscopy Mielczarski et al. (1995)
have s h o w that two major processes take place at the mineral interfaces: the interaction
with water and oxygen resulting in the formation of the oxidation products which are
mainly hydrophilic, and, the adsorption of xanthate producing different types of
hydrophobic surface products.
Figure 4.1. la shows that the rate of xanthate adsorption on synthetic enargite can be
explained in terms of an ion exchange mechanism. As the hydrophobic species is
continually being formed and precipitated on the enargite surface, it is obvious that
chernical reactions are not restricted to the formation of the surface monolayer. .As the
precipitation continues, the difisional rate will decrease such that the time required for
the deposition of each successive layer will increase. As cm be seen at low surface
coverage diffisional effects are negligible and the equilibrium state is rapidly attained. At
high surface coverage, difision of the reactants becomes the controlling factor and
equilibrium times are much longer. Figure 4 . 1 . l b reveals that xanthate adsorption on
copper ions from the enargite sufice and the availability of oxygen. As mentioned earlier.
water, open to the atmosphere, is nonnally saturated with oxygen to the extent of 8 mg/l
at room temperature and no attempt was made to de-aerate either the xanthate solution, or
the sarnple pnor to the adsorption test. It is therefore assumed that oxygen was present
both in the liquid phase and adsorbed on the solid surface. It is also possible that the
surface coverage is not uniforrn, and fresh sites may still be available. Between the
equilibriurn concentrations of 1.22 and 28.75 mg/l the adsorption density of xanthate
remains substantially unchanged, which suggests that the difision of xanthate through the
existing layer to react with the cupric ion at the enargite surface becomes the rate
controlling factor. Due to the large dserence in molecular sizes (1 -4 for oxygen and 5 A
for xanthate, Fuerstenau et al. 1990), the diffusion rate of the xanthate must be very slow
cornpared to oxygen. Hence as the adsorbed Iayers increase the oxygen difision will only
be slightly Sected in cornparison to the xanthate. Finally. as the concentration of xanthate
increases further, the adsorption density increases again. The siope of this part of the
c u v e is much lower than for the initial adsorption where large increases in the equilibrium
concentration are required to bring about smali increases in the amount adsorbed. This
also supports the hypothesis that xanthate diffusion is the rate controlling factor, however.
the main factor is assumed to be the slow diaision of xanthate ions.
Desorption tests reveded that it was not possible to remove adsorbed xanthate fiom
the surface with pure water. Since cuprous xanthate is tiighly insoluble in water thus it is
not surprising that no desorption was obtained with water. As a result of the desorption
tests it is also suggested that the adsorption is a chemisorption process.
Either a metal xanthate or a dixanthogen c m form on the sulphide minera1 surface to
act as the hydrophobic species when xanthate is used as the collector. The correlation
benveen mineral semiconductor type and the collector species found on the surface was
generalized by Ackerman et al. (1987). Infrared spectroscopy by these authors indicated
that, f i e r reaction with xanthate, the n-type semiconductors, chalcopyrite and pyrite.
p-type
semiconductors, chalcocite, bornite and covellite, were found to show only the
characteristic peaks of cuprous isopropyl xanthate. The solubilization of metaf ions fiom
the mineral also plays an important rote here. The solubility of copper fiom chalcopyrite is
substantial (Ackerman et al. 1987). These solubilized ions c m cause the rapid oxidation of
xanthate to dixanthogen. This was confirmed in the work by Allison et al. (1972) which
showed that dixanthogen is formed as the principal product of reaction on those minerals
that, in a solution of xanthate, assume a rest potential greater than the equilibrium
42.2 Flotation
of 3.991 mg/m2, which is then required for a high notation recovery. Any increase in
adsorption density below this point results in an increase Ui flotation recovery, however,
above this point the increase in adsorption density has no sigdicant effect on the notation
recovery.
Flotation results indicate that enargite does not possess a degree of native floatability.
To explain this behaviour, it is necessary to consider the crystal structure of enargite. If
one considers a mineral surface to be composed of rnainly sulphur anions. it is reasonable
to assume that the surface effects are iduenced to some extent by the propenies of
sulphur because elementai sulphur is highly water repellent and very easily floated without
the aid of a collector. This, however, is not the case for enargite, as Figure 4.1.2 indicates
very small floatability without collector. The crystal structure of enargite shows that the
sulphur atoms are not initially accessibie but prolonged oxidation changes the minerai
structure by breaking sulphur and arsenic bonds which results in arsenic oxides remaining
at the surface (Plaksin 1959). Complete floatability of dl particles was not reached since
frother was not used in any of the flotation tests. The absence of a frother eliminates any
possibility of frother-mineral and frother-collecter interaction.
4.2.3
In this investigation attempts were made to establish the effect of sodium cyanide on
the adsorption and flotation of synthetic enargite. Cyanide is the most common depressant
used in sulphide flotation. The desorption of xanthate Eorn the synthetic enargite surface
can be expiained by the solubility of cuprous xanthate in the cyanide solution. The
(4.2.3.1)
The complex Cu(CN)JS is the final complex. Wark and Cox (1934) caicuiated the free
research is 2.55 mgll [Cw.The tiee cyanide present foms the complex Cu(CN)JU from
the available cuprous xanthate. Figure 4.1.1.1 shows that at this free cyanide
concentration, 93.5 percent of xanthate is removed within 1 minute. At the sarne
conditions the contact angle was below 13O (Figure 4.1.4~).These results show that there
is sufficient free cyanide ion to depress synthetic enargite.
According to Glembotskii (1972) cuprous-xanthate is moderately soluble in cyanide
solutions and its solubility increases with an increase in cyanide concentration. According
to this mechanism Figure 4.1.1.1 demonstrates the rapid removd of xanthate from the
synthetic enargite surface. The reaction is rapid since there is no difision involved. The
minimum point represents the depletion of cyanide, after which a small arnount of cuprous
xanthate reprecipitates. The rate of readsorption is very slow due to the formation of
cyano-copper complexes, preventing the frther formation of cuprous xanthate. Even if
cuprous xanthate is formed, the addition of cyanide will dissolve the copper xanthate.
Thus, the depression of synthetic enargite appears to be very stable and the role of cyanide
strong cyanide complexes nor insoluble simple compounds. As a resuit arsenic xanthate
may not be present on the surface of synthetic enargite. Results of
IR studies on the
Cyanide and cyanide complexes rnay be adsorbed on the synthetic enargite surface thus
preventing the adsorption of xanthate on the surface (Wang 1989).
The increased cyanide concentration increases the rate and extent of depression. The
time of cyanide depletion in adsorption tests (Figure 4.1.1.1) is identical to the minimum
flotation recovery (Figure 4.1.2. la) under the same conditions.
The increase in PAX concentration brings about a higher recovery of synthetic
enargite flotation for a fixed NaCN concentration as shown in Figure 4.1.2. lb. The
chemisorb on the mineral surface forming a film of copper sulphide and releasing xanthate
ions into the solution- In the case of conditioning the minera1 in sodium sulphide solution.
the surface properties of enargite are modified by the chemisorption of the sulphide ions
and the adsorption of xanthate could not take place. The hydrophobic entity responsible
for flotation of synthetic enargite is cuprous xanthate. which can be formed at reduced
4.2.5
Effect of KMnOd
The results of the study that was made on the action of potassium permanganare on
synthetic enargite are presented in Figure 4.1.1.3. This figure shows the reaction between
xanthate and permanganate results in the formation of dixanthogen and hydrated foms of
reduced manganese oxides as observed by RineIli et al. (1980). The tests perfonned in the
present work do in fact indicate a strong reaction between xanthate and permanganate.
Figure 4.1.2.4a shows that an increase in ffiIMnO~concentration decreases the flotation
recovery. Also, with an increase in pH at any concentration of permanganate, there is a
decrease in recovery (Figure 4.1 -2.4b).The formation of stable hydroxides explains the
increase in enargite depression at high pH.
The result of the effect of potassium permanganate on adsorption density of PAX on
synthetic enargite shows that potassium permanganate exerts some action on the synthetic
enargite surface because the adsorption density decreased for oxidized synthetic enargite.
The oxidizing power of permanganate causes variations in the surface state of the enargite
by augmenting the spontaneous oxidation phenornena that occur when synthetic enargite
is exposed to air and water. The permanganate-enargite interaction can also be explained
by the reducing action of the sulphide ion as the reducing agent, and the formation of
arsenic oxides and copper hydroxide (Nakazawa and Iwasaki 1986). Therefore, xanthate
ions can not be completely adsorbed on the minera1 surface due to the precipitation of
hydrophilic forms of these types on the surface. Although xanthate ions stiil adsorb on the
minera1 in this condition. The hydrophilicity caused by the oxide films exceeds the
hydrophobicity induced by the collecter adsorption on surface. The action of
permanganate on synthetic enargite surface was observed dunng test procedures. During
the tests there was a colour change of both the solution and the mineral surface dunng
conditionhg with permanganate. This can be explained by the formation of hydrated
oxides as mentioned earlier.
4.2.6
Copper is always present in a solution with ground copper ores. It can corne fiom the
dissolution of copper oxide or sulphide minerals and is facilitated by the acidic nature of
most copper ores. CU*-, where present in the flotation pulp, can serve as an activator
(Ackerman et al. 1987). As shown in Figure 4.1.1.4, the addition of 25 mg/l copper
sulphate causes the adsorption density of enargite at pH 9 to be increased substantially.
The marked activation of synthetic enargite by copper sulphate is due to the selective
adsorption of Cu(I1) ont0 the arsenic sites forming the stable assenites, Cu3Asand CuzAs2.
This is supported by what is reported by Remy (1956) that both Cu(1) and Cu(I1) fom
stable arsenides. This same result was supported by Guongming and Hongen (1989).
Since copper arsenide is floated well with xanthate (Nakazawa and Iwasaki 1986). then
copper arsenide formation might improve the floatability of synthetic enargite. Generally
speaking, cupric ions activate the flotation of enargite, make the xanthate ions again be
adsorbed on enargite.
Figure 4.1.2.5 shows that an increase in cu2* concentration increases the enargite
recovery up to a concentration of 25 m g . However, a M e r increase in copper suiphate
concentration may not increase the notation recovery due to the precipitation of the
collector by excess copper ion in solution (Rogers 1976).
4.2.7
Effect of pH
The addition of aikali changes the concentration of hydrogen and hydroxyl ions in a
solution, and may also change the concentration of coilector species and the concentration
of heavy rnetal ions (Rogers 1976). As the relationship between pH and adsorption density
shows, the adsorption density did not change with the change in the concentration OF
hydroxyl ion in the range of pH 6 to 9. Therefore, there is no relation between the
concentration of hydroxyl and xanthate ions in this range, which may niggest the ease of
formation of the copper xanthate on the surface from the readily ionized xanthate.
However, there is a decrease in the adsorption density above pH 9 at PAX concentrations
of 20 and 50 rngA (Figure 4.1.1.5b). This is due to the increasing concentration of
hydroxyl ions, the decomposition of the collector and the formation of hydrophilic metal
hydroxides. These ions will take up sites on the mineral surface, leaving fewer for the
xanthate to attach to. This also probably reflects the lower solubility of copper at higher
p H values (Ackerman et ai. 1987) and aiso the decreased stability of copper xanthate at
higher pH values (Hepel and Pomianowski 1977). It should be noted that the nature of the
reaction products does not Vary with pH of the solution nor with the chah length of the
xanthate homologue used (Allison et al. 1972).
recovery both for NaOH and Ca0 regdators up to pH I 1 as shown in Figures 4.1.2.3a
and 4.1.2.3b. The reason for synthetic enargite being floated at high pH values is due to
the stability of cuprous xanthate relative to cuprous hydroxide, which have stability
constants of
5 . 2 1~0 ~ ~and
'
2 x IO-'', respectively (Fuerstenau et al. 1985). A sharp
4.2.8
Effect of Aeration
The minera1 flotation depends maidy on the collecter concentration in the pulp and
the oxidation extent of the mineral (Leja 1982). To investigate the effect of air oxidation.
flotation tests were carried out at various aeration time at pH 9. As s h o w in Figure
4.1.2.6, an increase in aeration time decreases the flotation recovery till it reaches a steady
state after 60 minutes. The results of a dissolution experiment (Table 4.3) showed that
synthetic enargite was susceptible to oxidation and liberated copper and arsenic ions upon
oxidation. The flotation results suggest that synthetic enargite will not stay floatable under
oxidizing conditions even if the rnetal ions are released in the solution. This is because the
surface of oxidized enargite consists of copper hydroxide and arsenic oxides; that is to Say.
copper ions, which are generated by an anodic reaction, react with hydroxyl ions
generated by the reduction reaction of oxygen at cathodic sites of enargite leading to the
precipitation of copper hydroxide (Nakazawa and Iwasaki 1986). However, synthetic
enargite may be floatable to some extent if it is not mongly oxidized as shown in Figure
4-1.2.6.
a cathodic
+ 20H'
-+XZ+ 2e'
(4.2.9.3)
and/or: the formation of a thiol compound with a metal component of the mineral, e g ,
MS+2X+MXz+S+2e'
(4.2.9.4)
The sulphur component of the mineral surface can aiso be oxidized to sulphur-oxy anions
such as sulphate or thiosulphate in reactions leading to the formation of metal-thiol
compounds, e.g.,
(4.2.9.5)
Processes such as reactions (4.2.9.4) and (4.2.9.5) can take place via separate steps
which may occur at dEerent tirnes. For example, reaction (4.2.9.4) could involve
(4.2.9.6)
and, when the collecter is added, a methatical reaction couid take place,
(4.2.9.7)
The latter process is often considered as a chemical or ion exchange mechanism. However.
since the initial oxidation is a corrosion-type process, it is readily accomrnodated within
floatability. By comparing these results with the results obtained in Figure 4.1.3 it can be
seen that significant flotation ocnirs at sufiace coverages at which the adsorption density
of chemisorbed xanthate is complete. A metal xanthate could be formed by interaction of
Cu+X-CuX+e'
(4.2.9.8)
where:
Eo = -0.719 V
E = -0.719 - 0.0591 log [ 9 . 9 ~ 1 0 ' ~ ]
E = -0.432 V
VS.
SHE
E = -0.724 V
VS.
SCE
The flotation edge of synthetic enargite is sufficiemly negative to conclude that cuprous
xanthate is the active hydrophobic species. A 24.5 percent floatability at -485 mV vs. SCE
can be reasonably well comelated with the direct reaction between synthetic enargite and
xanthate ion. Floatability was low below -3 10 mV. but became complete between -3 10
and -58 m V at the pH level tested. It seems unlikely that this product could be
dixanthogen, for the equilibriurn potential of the xanthatddixanthogen couple for 20 mg/i
( 9 . 91~
0-5 M) PAX from the relation given by Hepel and Pornianowski (1977) was
calculated to be -164 m V vs. SCE. Thus the significant participation of dixanthogen in the
enargite-xanthate interaction seems improbable. It is assumed that, in accordance with the
results of adsorption tests, the principal reaction product responsible for Botation is the
cuprous xanthate. With increasing potential, the floatability fnher decreased due to the
decomposition of cuprous xanthate. Roos et al. (1990) noticed that the decomposition of
cuprous xanthate species takes place above O mV vs. SCE.
4.2.10
effects are not influenced by the properties of sulphur. The pH of the solution did not
affect the contact angle value to any large extent from pH 6 to 9. In the presence of
sodium cyanide contact angle values were found to be dependent on the pH and the
concentration of sodium cyanide at constant xanthate concentrations. Wark and Cox
(1934) have shown that the fkee cyanide concentration is dependent on pH. According to
them the concentration of free cyanide increases with pH which in tum makes an increase
in the depression effect of cyanide. As mentioned earlier, the concentration of free cyanide
for 15 mgA NaCN at pH 9 and pH 11 are 2.55 mgfi and 7.8 mg/l, respectively. The very
srnail contact angle obtained at hi@ sodium cyanide concentrations suggests that the
reaction of cyanide with cuprous xanthate is very rapid, as indicated by the adsorption and
flotation results.
4.2.11
Infiared spectroscopy is probably the most widely used technique for direct
examination of products on the surface. This has been used to provide information both on
the nature of collector/mineral reaction species and dso on the oxidation products on a
surface prior to reaction. The results of IR studies of the surface composition of enargite
after adsorption show that the principal absorption bands of synthetic enargite contacted
with potassium amyl xanthate at pH 7 occur at 875, 1030, 1205 and 1260 cm? As the
principal bands of cuprous amyl xanthate occur at 1030, 1205 and 1260 according to
Ailison et al. (1972). it can be concluded that these three bands are due to adsorbed
cuprous xanthate. Moreover, cuprous xanthate which has only one C-S bond also shows a
band at 875 cm-' (Little et al. 1961). The remaining bands can be attributed to the
synthetic enargite surface and to the Nujol oil. These results support the premise that
cuprous xanthate is the species primarily responsible for flotation of enargite in the
presence of xanthate.
4.2.12
In their work Ackerman et al. (1987) have shown that the solubility of 'UC
fkom the
dixanthogen. They noted that the relatively large amounts of copper ions released
especially fiom chalcopyrite (21 mgA) would generally facilitate the conversion of
xanthate to dixanthogen. The solubility of synthetic enargite was 4.1 mg/l CU*- (Table
4.3). This value is much less than the solubility of the chalcopyrite sample used which was
19.8 mg/l CU*- a the sarne conditions. The results mle out the oxidation of xanthate to
dixanthogen, but suggest the production of cuprous xanthate on the synthetic enargite
surface by the rnechanism explained in section 4.2.1. Data obtained for the solubility of
aerated synthetic enargite shows a decrease in solubility d e r 2 hours aeration. It can be
concluded that the copper ion might be precipitating as copper hydroxide. On the other
hand arsenic ion concentrations must have decreased by adsorption on the copper
hydroxide precipitate (Nakazawa and Iwasaki 1986).
The pH at which the surface has zero charge is referred to as the zero point of charge.
In other words, assuming the potentiai differences due to dipoles remain constant, the
total double layer potential is considered zero. Zero point of charge of a minerai is an
important characteristic because the adsorption of various organic and inorganic ions will
be govemed by the location of the solution properties (as pH) with respect to the zpc
(Somasundaran 1975). The resuits of this investigation using the adsorption of potential
determining ions technique (Yen, W.T.) show that the value of zpc for synthetic enargite
is 3 . It was noted that the collecter is adsorbed at the synthetic enargite surface above pH
3. Xanthate ions are adsorbed by spedic chernical interaction, chemisorption, above the
zero point of charge (Fuerstenau et al. 1990). Chernisorption would have to occur by
interaction of the xanthate with surface metal ion, fonning, copper xanthate.
4.2.14
The rest potential of an enargite electrode in xanthate solution was measured and
compared to the xanthatddixanthogen redox potential. As the rest potential measurement
would predict, those rninerals giving rest potentials greater than this redox potentiai have
been shown by other techniques to form dixanthogen on the surface and those with lower
rest potentials, the metal xanthate (Allison et al. 1972). The rest potential of enargite
after 10 minutes in a 6 . 21o4
~ ~M solution of amyl and ethyl xanthate at pH 7 was
found to be -0.1 10 and -0.020 V vs. SHE, respectively. The reduction potentiai for the
couple xanthateldixanthogen in a solution of the same concentration for amyl xanthate was
calculated to be 0.030 V and for ethyl xanthate was 0.130 V. As the rest potential of
enargite is less than the corresponding equilibrium potential for the oxidation of xanthate
solution of the sarne concentration, it is suggested that cuprous xanthate is fonned as the
principal surface reaction product.
4.3
Conclusions
The present investigation provides some information on the flotation and depression
characteristics of synthetic enargite in the presence of potassium amyl xanthate .
The studies on the xanthate-synthetic enargite initially involved a study into the
adsorption of potassium amyl xanthate on the surface of synthetic enargite. The rate and
density of adsorption were examined as were the influence of other reagents (depressants)
in the system. The results concluded that xanthate has a very high adsorption affinity for
the synthetic enargite surface while no desorption was observed using water as a solvent.
It is suggested that
oxidation products on the surface of synthetic enargite. to forrn the highly insoluble
compound, cuprous xanthate, which precipitates on the synthetic enargite surface. Based
on an ion exchange mechanisrn the xanthate adsorption isothem suggests that cuprous
xanthate adsorbs on the synthetic enargite surface and the xanthate-enargite interaction at
high xanthate concentrations is controlled by the slow diffusion of xanthate anions to the
enargite surface. The influence of pH on xanthate adsorption is not afFected up to pH 9
but shows a substantial decrease in adsorption density at pH 12. This is due to the
formation of hydrophilic metai hydroxides on the synthetic enargite surface. The addition
Flotation tests were performed to evduate the floatability of synthdc enargite in the
presence of PAX. It was found that a maximum recovery of 79.3 percent was obtained at
a xanthate concentration of 50 mg/l.
The flotation of synthetic enargite was potentiai-dependent between -485 and +IO0 m V
vs. SCE. The onset of this potentiai region coincides with the direct reaaion between this
minerd and xanthate ions which results in the production of cuprous xanthate. Complete
floatability of aii particles was not reached since eother was not used in any of the
flotation tests. The decrease of flotation recovery above -58 rnV vs. SCE is due to the
decomposition of cuprous xanthate species.
Contact angle measurements confirmed that under mild alkaline conditions a
CHAPTER 5
Flotation Chemistry of Naturai Enargite
5.1 Resuits
5.1.1
Adsorption
rapid in the initial 30 minutes; accordingly, aii the following tests with natural enargite
were performed by agitation for one hou.
10 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 0 1 0 0 1 1 0 1 2 0
Adsorption T i m e (minutes)
Figure 5.1. la: The adsorption of PAX on naturai enargite as a fiinction of time at
20 mgil initial mthate concentration.
solution at various initial xantfiate concentrations was also obtained at pH 9 and belongs
to L type curves. This isotherm, presented in Figure 5.1. l b exhibits three dinerent regions.
At low residual concentrations (Iess than 1 mgA), the density of xanthate on natural
xanthate nom solution by naniral enargite. The second region in the range o f 1-1 9 mg/l is
a plateau, a Langmuir type plot, where the arnount of xanthate adsorbed remains refatively
constant. in the &al stage, M e r adsorption takes place (above an equilibrium
concentration of 19 mgA), representing a physicai adsorption region.
0.1
10
1O0
5.1.1.1
In order to study the effect of sodium cyanide on the pre-adsorbeci xanthate on the
natural enargite surface the xanthate solution concentration was maintained constant at 20
mg/l. The results obtained are presented in Figure 5.1.1.1 which show that the uicrease in
cvanide contact time resdted in the desorption of the xanthate fkom the nahval enargite
surface. At 15 mg[ sodium cyanide, a maximum 4 1 percent of xanthate is removed within
120 seconds. Mer 120 seconds readsorption takes place,
-C-CyanidcConc
= 10rng1l
-C C y a n i d c C o n s = I J m g l l
.....................
.....----.....
3 -5
.
..
..
1 .O
...
..
...
..
...
..
...
..
1
...
.
..
...
.
..
...
..
..
..
..
1O
..
..
..
..
..
.
..
...
..
-'---'----I
,
..
..
..
..
..
..
..
..
..
..
...
15
2O
adsorption density.
Test Conditions
Initial PAX Conc.=20.0 mg/L Conditionhg Tirne= 10 min.. p H 4 . 0
Adsorption Density mg/m2
First Conditioned With Depressant
Onguial
KhilnOo.50 mg/l
Aeration, 20 min,
NaCN. 15 mg/l 1 NazS. 10 mgll
2.859
1.978
2.484
1.907
1.926
A cornparison of the results shows that the effect of sodium cyanide at I O minutes
contact is higher on the pre-adsorbed xanthate on the natural enargite surface than on the
reverse ragent addition sequence.
5.1.1.2
The effect of sodium sulphide on the pre-adsorbed xanthate on the natural enargite
surface is s h o w in Figure 5.1.1.2. The results indicate that the increase in contact time
causes the desorption of xanthate fiom the natural enargite surface. For 10 rngA sodium
sulphide concentration there was a 20 percent desorption of ximthate nom the nanirai
enargite surface at 5 minutes. There was not much change after 5 minutes contact.
The effect of sodium sulphide was evaluated by conditioning the natural enargite
sample with sodium sulphide foiiowed by the xamhate addition. The results are given in
Table 5.1. The adsorption density at 20 rnfl xanthate concentration is 86.9 perceht of the
original adsorption density.
These resuits obtained show that the effect of sodium dphide is higher on the pre-
adsorbed xanthate on the natural enargite d a c e than the reverse ragent addition
sequence.
..
..
..
..
...
.
..
...
.
...
...
.
...
-C Sodium S v l p b i d e C o n c . - l m g l l
~SodiumSulphidcConc.=lOmglI
10
15
20
S o d i u m S u l p h i d e C o n t a c t T'imc ( m i n u t e s )
Figure 5.1.1.2: The effect of sodium sulphide concentration and contact time on the pre-adsorkd
.uanthate on natural enargite at pH 9 and 20 mgil PAX concentration.
5.1.1.3
adsorbed xanthate on the naniral enargite surface. After 2 minutes contact there is a
desorption of xanthate fiom the naturai enargite surface. A readsorption takes place at 5
minutes contact with no considerable change in adsorption density after that. After 20
..
..
......
..
K M n O , C o n c . = 2 5 rn g/l
C o n c . = 5 0 mg/]
+K M n O ,
Figure 5.1.1.3 : The &ct of KMnOj concentration and contact time on the pre-adsorbed on
na&
enargite at pH 9 and 20 mg11 P M concentration.
Table 5.1 presents the effect of KMnOI on the adsorption density of PAX on natural
enargite by pre-conditioning with potassium permanganate followed by xanthate addition.
The adsorption density for 20 mg/i xanthate solution is 66.7 percent of the original
adsorption density.
The results show that the effect of KMn04 on the xanthate desorption from the
natural enargite surface is stronger than the conditioning of the minera1 with permanganate
followed by xanthate addition.
5.1.1.4
Effect of pH on Adsorption
Figure 5.1.1 -4. The pH was varied fiom 6 to 12 with sodium hydroxide in a 20 mg/l
xanthate solution. The results show that the adsorption density remains constant f?om pH
6 to pH 9 and greatly decreases at pH higher than 9.
Figure 5.1.1-4: The &kt of pH on the adsorption density of PAX on nanual enargile.
density.
5.1.2
Rotation
Figure 5.1.2 shows the effect of coiieaor concentration on the flotation of natural
enargite at pH 9. The naturai enargite recovery increases very fast with increasing PAX
concentration to 20 mg/S reaching about 77 percent recovery at 30 mgA. More than 80
percent recovery is obtained at a PAX concentration of 50 mgil. A typical parabolic
relationship is demonstnited.
10
15
20
25
30
35
40
45
50
5.1.2.1
The effect of sodium cyanide concentration and contact time on the flotation recovery
of natural enargite is given in Figure 5.1.2.1. The results show that the flotation recovery
decreases to about 23 percent with a sodium cyanide concentration of IS mgIl and contact
time of 2 minutes. Depression is not stable and after a period of 5 minutes of contact t h e
with cyanide the flotation recovery starts to inaease slowly to 33.5 percent at 20 minutes.
By conditionhg in 10 mg/l sodium cyanide solution, the naturai enargite recovery was
37.5 and 53.O percent at 2 minutes and 20 minutes contact tirne, respectively.
..
.............
-+- S o d i u m C y r n i d c C o n c . = l S
.
mgil
Figure 5.1.2.1: The effect of sodium cyanide concentration and contact time on the
floatability of naturai enargite at pH 9 and 20 mg/l PAX concentration.
Test Conditions
%R
Onginal
NaCN. 15
71.25
5.1.2.2
ma
Na2S. IO mgA
KMn04.50 mR/1
Aeratioe 20 mia
57.83
47.35
5 1.25
47.75
The effea of sodium suiphide concentration and contact time on the notation
recovery is presented in Figure 5.1.2.2. The results show that recovery decreases with
increasing sodium sulphide concentration and contact tirne. Flotation recovery decreased
to 62 and 54 percent for sodium suiphide concentrations of 5 and 10 mgA, respectively, at
20 minutes.
.,
..
..
..
..
.
..
.
..
..
.
.
.
.
..
..
..
..
..
..
..
..
..
..
-C- S o d i u m S u l p h i d c C o n e = 5 m g I l
Sodium Sulphtde C o n c = I O m g I l
I
i
..
..
Figure 5.1.2.2: The effect of sodium sulphide concentmion and contact tirne on the
floatabiiity of narurai enargite at pH 9 and 20 mg/l PAX concentration.
The effect of sodium sulphide on the naturd enargite surface was also investigated by
conditionhg this minerai with Na2S followed by adding xanthate and then performing
5.1.2.3
Effect of pH on Fiotation
The effect of pH on the naturai enargite flotation was conducted with a 20 mgil PAX
solution. Figure 5.1.2.3shows that with increasing pH the floatability of naturd enargite
remains constant at 72 percent in the pH range of 6 to 9.The flotation recovery decreases
sharply for solution pHs higher than 9. About 59 and 22 percent of nahiral enargite is
- ........ -- P A X C o n c . = 2 O m g l l
I
...................-.......................
I
5.1.2.4
0.1
10
K M n 0 4 Concentration ( m g I l )
100
As cm be seen From Table 5.2, by conditioning the natural enargite sample in 50 mg11
KMn04 solution foiiowed by the xanthate addition and then flotation, 47.35 percent
5.1.2.5
Figure 5.1.2.5 shows that the recovery of natural enargite decreases remarkably with
aeration time. Under the test conditions, recovery decreases to about 30 percent in 2
hours. The decrease in recovery is very smaii between 1 hour and 2 hours aeration.
20
4O
60
8O
100
120
5.1.2.6
100
200
Potcntiai ( m V v s . SC E)
Figwe 5.1.2.6: Relationship baween flotation recovery and pulp potmial for
naturai enargite at pH 9 and 20 mg/l PAX concentration.
5.1.3
Adsorption-Rotation Relationship
The natural enargite adsorption-flotation relationship is presented in Figure 5.1 -3. The
natural enargite flotation recovery uicreases rapidly with increase in the xanthate
adsorption density in the range of zero to 1.408 mg/m2, whiie the floatability increased
fiom zero to 62.15 percent. As the adsorption density increases beyond 1.408 mg/m2,the
increase in floatability is slower. At an adsorption density of 7.484 mgjm2 or 50 mg/i initial
5.2 Discussion
The adsorption and flotation tests on natural enargite were perfonned in order to
compare the results with that of synthetic enargite. However. surface oxidation and pyrite
impurity contained in the natural enargite appear to have some effect on its adsorption and
flotation behaviour.
xanthate as the principal hydrophobic entity on the natural enargite surface does not
preclude the possibility that both cuprous xanthate and dixanthogen may be present
together on its surface. Thus the adsorption of xanthate on naturai enargite produces
cuprous and dixanthogen complexes. These hydrophobic species have also been observed
on tennantite (a copper arsenic sulphide) which contained pyrite as an impurity
(Mielczarski et al. 1995).
The desorption of xanthate fkom the nahiral enargite surface c m be explained in terms
of the solubility of cuprous xanthate in the cyanide solution and the formation of the
compiex Cu(CN)jmas the predominant species. Cyanide or cyanide complexes may dso be
adsorbed on the mineral surface. Because of the pyrite irnpurity, on the other hand,
cyanide cm react with dixanthogen forrning an aikyl thiocyanate as an intermediate and
then decomposing to diaikyl mono sulphide and thiocyanate. The d a c e properties of
natural enargite are aiso modified by the chemisorption of sodium sulphide ions and
xanthate adsorption could not occur. The reaction between permanganate and xanthate
results in the formation of hydrated f o m of reduced manganese oxides. The oxidiing
power of permanganate on the naturai enargite surface is also due to the reducing action
of ferrous iron in the mineral, and the formation of hydrated oxides of iron on the sudace.
The adsorption density for naturai enargite remains constant fkom pH 6 to pH 9 and
decreases at the higher pH values. The associated pyrite contributes to the dirninishing
adsorption density of natural enargite at pH higher than 9.
Naturai enargite rnay be floated at reducing potentials. The major hydrophobic species
of natural enargite is cuprous xanthate and its formation could occur at reduced potentials.
At high reducing potentials, the formation of dixanthogen may be inhibited if pulp
potentials in flotation are below the rest potentiai of the X E 2 couple which was
calculated to be -1 64 mV vs. SCE.The formation of cuprous xanthate, on the other hand,
occurs at potentiai ranges appreciably below this. It was noticed that natural enargite is
still floated at potentials above -164 mV up to +14 mV vs. SCE. This shows that
dixanthogen is the hydrophobic entity responsible for the flotation of natural enargite in
this range. Therefore, it is concluded that both cuprous xanthate and dixanthogen act as
the hydrophobic species on the natural enargite surface.
5.3 Conclusions
- The results of adsorption and notation studies indicate that a maximum recovery of 83 .O
percent is obtained ai a xanthate concentration of 50 mgfi. This initial xanthate
concentration corresponds to an adsorption density of 7.484 m g / d .
- Sodium cyanide and potassium permanganate have a stronger depression effect than
sodium sulphide on the natural enargite.
- It was shown that Eh has a controiling iniluence on the flotation of natural enargite.
CHAPTER 6
Flotation Chemishy of Chalcopyrite
6.1 Results
6.1.1
Adsorption
Figure 6.1. La shows the relationship between the adsorption density of PAX on
chalcopyrite and retention time for the solution concentrations of 20 and 50 mgll PAX at
pH 9. Results indicate that the adsorption density of both solution concentrations reached
a plateau at 120 minutes retention time. Thus, the agitation t h e s in the subsequent tests
were ail rnaintained at two hours.
Adsorption T i m t (minutes)
presented in Figure 6.l.Ib. This isotherm belongs to the L type curves. The first part of
the curve ( 1 S-6 mgIl equilibriurn xanthate concentration) follows a Freundlich type
isotherrn and the second part of the curve (6-122 mg/I equiiibnum xanthate concentration)
gives a Langmuir type plot. Findly further adsorption takes place, but at a Iower increase
per unit change in concentration than before.
10
100
1O00
6.1.1.1
o f contact. After 120 seconds readsorption takes place, and withi 20 minutes the
adsorption density recovers to 72 percent of its original value. At 15 mgA sodium cyanide
concentration, there is a desorption of xanthate from the start of sodium cyanide addition
to 2 minutes which is about 80 percent of its original value followed by xanthate
readsorption.
The effect of sodium cyanide on the xanthate adsorption, evaluated by conditioning
the chalcopyrite sample in cyanide solution followed by xanthate addition and flotation. is
given in Table 6.1. The results show that the adsorption density at 20 mg/l xanthate
concentration is about 80.4 percent of the original adsorption density.
A cornparison of the results indicates that pre-conditioning of chalcopyrite with
cyanide for 10 minutes has a higher depression effect than the effect of cyanide on the preadsorbed xanthate.
Table 6.1: The egect of depressants on the mthate adsorption on chalcopynte.
Original
2.789
Test Conditions
Initial PAX Conc.=20.0 mg/I. Conditioning Tirne=1O min.. pH=9.0
Adsorption Density mdm'
First Conditioned With Depressant
Aeraion. 20 min.
NaCN, 15 mR/I Na2S. 10 mg/l
m4.
50
ma
2.242
1.044
1.958
2.131
10
15
N a C N Contact T i m c ( m i n u t e s )
Figure 6.1.1.1 : The effct of NaCN concentration and contact tirne on the pre-adsorbeci
m t h a t e on chaicopyrite at pH 9 and 20 mgil PAX concentration.
6.1.1.2
sodium sulphide solution 62 percent of the xanthate is desorbed fiom the surface. The
xanthate desorption continued up to 20 minutes contan time. reaching about 25 percent
of the onginai adsorption density.
...
-5
...
.
...
,
...
P
.
.
..
...
...
...
..
..
..
..
..
...
-t- S o d i u m S u l p h i d e C o n c - 5 m g f I
IS o d i u m S u i p b i d c C o n c
10
.
.
.
.
.
.
.
.
Figure 6.1.1.2: The &cct of sodium sulphide concentration and contact Ume on the
pre-adsorbeci xanthate on cbalcopyrite at pH 9 and 20 mgll PAX
concentration.
effea on the pre-adsorbed xanthate on the chalcopyrite surface than the reverse reagent
addition sequence.
Figure 6-1-13 shows the effkct of permanganate contact time on the pre-adsorbed
xanthate on chaicopyrite. The desorption of xanthate is rapid from the chalcopyrite surface
during the initiai two minutes of contact. Mer 5 minutes readsorption takes place and the
adsorption density recovers to 90 and 77 percent of the original adsorption density at 20
minutes contact for -4
K M n O 4 Contact T i m e ( m i n u t e s )
Figure 6.1.1.3:The &en of KMnOI concentration and contact time on the pre-adsorbed
xanthate on chalcopyrite at pH 9 and 20 mgA PAX concentration.
6.1.1.4
Effect of pH on Adsorption
.......
-0-
P A X C o n c . = 2 0 mg11
...&..........
...........
6.1.1.5
The effect of aeration on the xanthate adsorption is presented in Table 6.1. The
adsorption density of xanthate on chalcopyrite is about 77 percent of the original
6.1.2
Flotation
.......
4...
.......................................... .........................................
I
20
40
60
80
100
The effect of copper sulphate on the flotation recovery of chalcopyrite was also
studied at pH 9 and 20 r
n
d PAX concentration. The results showed that copper sulphate
had no measurable effect on the flotation recovery of chalcopyrite.
6.1.2.1
sharply with the cyanide addition to the initial 2 minutes contact, at which time it reaches
the lowea flotaiion recovery. Mer this point the flotation recovery gradually increases. A
flotation recovery of about 42 percent at 20 minutes occurs in a 20 mg/l NaCN solution.
. -.-.-..-*-............
- ........
----..........
.
.
.
..
..
+N a C N C o n c
=15 mgll
-*..
.
.
.
.
.
.
.
...
...
...
..
..
..
..
.. ..
.......................................................,.....................................
.
-
10
..
..
O
O
.
.
.
.
.
-..-;.......................
..
.........-...-.........1 ..............
.
..
10
15
20
Figure 6.1.2.1: The effct of sodium qanide concentration and contact time on the
the floatability of chahpyrite at pH 9 and 20 mgil PAX concentration.
The effect of sodium cyanide on the chalcopyn?e flotation by conditioning the minera1
sample in 15 rngh sodium cyanide solution followed by xanthate addition and flotation
shows that fiotation recovery decreases to 56.62 percent (Table 6.2).
Test Conditions
Initial PAX Conc.=20.0 rng/I, Conditioning T i m 10
~ mh. pHe.0
%R
Frst Conditioned With Depressant
Na2S. 10 mg/l
KMn04,50 mR/t
Original
NaCN. 15 mg/l
56.62
80.65
6.1.2.2
50.9 1
26.15
Aeration. 20 min.
67.44
is given in Figure 6.1.2.2.The results show that there is a decrease in notation recovery to
about 18 percent at 20 minutes contact for 10 m g sodium sulphide concentration.
..
-..
... .. ... ... ....
.-..-----------.....---..-**
..
..
..
..
..
..
.
.
.
.
.
.
.
.
.
.
..
.
.
.
.
.
.
.
.
..
..
.
. -cC- S o d r u m S u l p h i d c C o n e - 5 m g I l
;
:.
Sodrum S u l p h i d e C o n c = 10 m g / l
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
...
*-
1O
Sodium S u l p h i d e Contact
15
-..
20
Time ( m i n u t e s )
Figure 6.1.2.2: The effm o f sodium sulphide concentration and contact time on the
fioatabilityof chalcopyrite at pH 9 and 20 mgA PAX concentration.
Na2S foliowed by xanthate addition and flotation is s h o w in Table 6.2. The flotation
6.1.2.3
Effect o f pH on Flotation
Figure 6.1.2.3shows the effect of pH on the chalcopyrite flotation Results show that
the flotation recovery of chalcopyrite does not siguficantly change in the pH range of 6 to
9. The chdcopyrite recovery is about 90-92 percent with 50 mgh PAX and 8 1-84 percent
concentrations. When Ca0 was used as a pH regulator it was alrnost without a perceptible
effect on the flotation of chalcopyrite and the resuits obtained were aimoa the sarne as
when NaOH was used.
6.1.2.4
o. 1
10
100
K M n O q Concentration (mg/])
Table 6.2 shows that 5 1 percent chalcopyrite recovery is attained by conditioning the
chalcopyrite sarnple in 50 mg/i
flotation.
The effect of permanganate concentration on the chalcopyrite floaiability was aiso
studied at pH values of 6 to 12. The results of these tests are presented in Figure 6.1.2.4b7
where recovery is plotted against pH
at
recovery does not change fkom pH 6 to pH 9, but there is a decrease in recovery at higher
pH values.
10 20 30 4 0
5 0 6 0 70 8 0 9 0 1 0 0 1 1 0 1 2 0
A tration T i m e ( m i n u t e s )
6.1.2.6
redox reagents. Figure 6.1.2.6 shows the effect of redox potentiai on chalcopyrite
floatability. At negative potentials below -260 m V vs. SCE a very low floatability (<20%)
is observed. The chalcopyrite floatability is increased to about 80 percent at - 1 50 m V vs.
SCE. At potentiais higher than +IO0 mV, the chalcopyrite recovery drops sharply,
reaching below 40 percent at +286 m V vs. SCE.
Potcntial (m V v s . S E C )
Figure 6.1.2.6: Relationship between flotation recovery and puip potenual for
chalcopyrite at pH 9 and 20 mg/l PAX concentration.
results show that there is a sharp increase in recovery to 90 percent at 7.088 mg/m2
adsorption density followed by a srnail increase in recovery to 92.75 percent at 1 1.O75
A d s o r p t i o n D c n s i t y (rn g l m ')
6.2
Discussion
6.2.1 Adsorption
Xanthate adsorption on chaicopyrite can be explaineci in tems of an ion exchange
mechanism. Figure 6.1.1b shows that an initial chernisorbed layer is fonned on the
chalcopyrite surface foiiowed by physicai adsorption of additional layers of xanthate.
Initially the adsorption density sises steeply, with an increase in the equilibrium
concentration of xanthate and reaches a value of 7.088 mg/m2 at a residual xanthate level
of 6.58 rng/l. According to the ion exchange mechanism of adsorption, the reaction rate is
controlled by the diffusion of copper ions from the chaicopyrite surface and the availability
of oxygen. Oxygen, nomally available in the environment, can react with the ions on the
rnineral surface and act as a bridge or iink between these sites and the surfactant. Between
the equilibriurn concentrations of 6-58 and 122.29 mgA the adsorption density of xanthate
remains relatively unchanged, which suggests that the diffusion of xanthate through the
existing layer becomes the rate controlling factor. Finally, as the concentration of xanthate
is further increased, the adsorption density increases again although the slope of this part
of the curve is much lower than the slope of the initial adsorption region.
A rnetal xanthate or a dixanthogen can forrn on the sulphide rnineral surface and act
as the hydrophobic species when xanthate is used as the collecter. On the other hand,
cuprous xanthate will fonn more readily than ferrous xanthate. Results of IR studies of the
chalcopyrite surface after adsorption of amyl xanthate indicated the formation of
dixanthogen, and cuprous amyl xanthate surface species (Mielczarski et al. 1995). The
i-ed
spectroscopy data by Ackerman et al. (1987) indicates that the surface of the n-
6.2.2
Flotation
PAX is given in Figure 6.1.2. The higher xanthate concentrations result in better flotation
up to 50 mgil concentration. This concentration corresponds to an 11.075 mg/m2
adsorption density of xanthate on the chalcopyrite surface. The chalcopyrite adsorptionflotation relationship shows that the increase in adsorption density to 7.088 m g m 2
corresponds to 90 percent recovery. However, a maximum recovery of 92.75 percent is
obtained at the adsorption density of 11.075 mg/rn2. Copper sulphate did not exert any
effect on the notation recovery of chalcopyrite. The aciivating action of copper sulphate is
due to cu2+and hence it does not directly affect the flotation recovery of chalcopyrite
which is possessive of copper sites.
6.2.3
Effect of NaCN
SCN. Cyanide can reaa initiaiIy with dixanthogen forming an dkyi thiocyanate as an
intermediate product and finally decomposing to diaikyl mono sulphide and thiocyanate
(Leja 1982):
+ (RCS)2S + S C N
(6.2.3.1)
(6.2.3.2)
It is also well known that cyanide ions form extrernely stable complex ions with iron
(Wang 1989), and therefore it is plausible that there is difision of cyanide ions through
the xanthate layer which evennially react with iron hydroxide at the mineral surface and
retard the readsorption of xanthate. A11 these factors wil1 either reduce or stop the
chernisorption or oxidation of xanthate. and therefore depress the notation of chalcopyrite.
pulp. Consumption of cyanide is very fast by copper. iron and dixanthogen. Afier
consumption of ail the cyanide in the solution the formation of dicanthogen starts again,
after which flotation is regained. The t h e of cyanide depletion in adsorption tests (Figure
6.1.1.1)is identicai to the minimum flotation recovery (Figure 6.1.2.l),under the same
conditions. The increased cyanide concentration increases the rate, and extent of
depression. Therefore, the concentration of W is critical, the excess resulting in
chaicopyrite depression. However, chaicopyrite wiil tolerate an increase in cyanide
concentration before depression becomes marked.
6.2.4
The application of a modifjmg agent such as sodium sulphide, a reducing sulphurcontainhg agent, as a sulphide mineral depressant was evaluated. It is believed that the
mechanism of this depressing agent is mainiy due to its reducing property. A strong
indication was supported by an electrokinetic snidy of Kydros and Matis 1995. The HSand s2- ions resulting from the alkaline hydrolysis of Na2S.9H20 solutions reaa with heavy
met& to produce low solubility compounds. In addition, these ions are unstable in
aqueous solutions since they are easily oxidized to S0 , SOI*- , and s 0 d 2 - ions (Castro
1979). These two chernical characteristics of sulphide ions m u s be considered in the
as a depressant, copper sites on the chalcopyrite surface are involved, that is, due to the
stability of copper suiphide, chemisorption of sulphide ion on that site wiil occur. These
two effects result in chakopyrite exhibiting greater sensitivity to sodium suiphide than
sodium cyanide (Fuerstenau et al. 1985).
6.2.5
Effect of KMnOs
The test results with KMnO4 as a depressant are presented in Figure 6.1.1.3, where
adsorption density is plotted against permanganate contact time at 25 and 50 mg/l -O4
concentrations. The depression action of permanganate Licreases with time up to two
minutes and after that the xanthate adsorption density increases within 5 minutes and then
with a slight increase to 20 minutes. With increase in permanganate concentration there is
a decrease in xanthate adsorption density and notation recovery. Also with increase in pH
at any concentration of K M 4 there is a decrease in recovery. The permanganate and
xanthate interaction can be ascribed to the formation of dixanthogen and hydrated forms
of reduced manganese oxides as demonstrated by Rinelli et ai. (1980). Chalcopyrite,
however, is also depressed at alkaline pH, when the oxidation of the xanthate to
dixanthogen is very weak. This shows the strong depression effect of manganese oxides
on chalcopyrite. The role of dixanthogen is only to weaken this depression effect. The
permanganate-chdcopyrite interaction can be explained by the reducing action of the
ferrous iron in chalcopyrite and the formation of hydrated oxides of iron. The depression
of pyrite in the presence of ~ e was
~ ' observed by Fuerstenau et al. (1968).The formation
of copper hydroxide on the surface of chalcopyrite should also be considered as a
hydrophilic entity.
6.2.6
Effect o f p H
There exins a close relationship between the solution pH and the pulp potential
because hydrogen ions are always present in aqueous solutions. Potentials generally
decrease with increasing pH (Cheng and Iwasaki 1992). Fiotation of sulphide minerals is
readily aEected by the change in pH. In general, floatabilities are strongiy depressed in
alkaline solutions. This is due to a number of phenornena. Firsty, hydroxyl ions. perhaps
through the formation of metal hydroxides, make the surfaces of sulphide minerals
hydrophilic. Secondly, from an electrochemical point of view, pulp potentiais shift towards
more cathodic when pH is more alkaline, and consequently retard the oxidation of
xanthate ion to dixanthogen. Thirdly, minerals rnay undergo decomposition at cathodic
potentials, and their surface properties are changed, thereby afFecting their floatabilities.
Fuerstenau et al. (1968) stated that the decrease in the adsorption density at higher pH
values is due to the decomposition of the dixanthogen at high alkaline media. The effect of
pH on flotation recovery of chalcopyrite shows that the recovery remains nearly constant
from pH 6 to pH 9 but decreases above pH 9 with a sharp decrease at pH 12. The slow
formation rate and decreased stability of dixanthogen in the more alkafine solutions is
responsible for the decline in the flotation recovery. This also reflects the lower solubility
of copper and decreased stability of copper xanthate at higher pH values (Ackerman et al.
1987). Since danthogen and cuprous xanthate are the effective hydrophobic species for
some effeas on floatability. The flotation tests were carried out to investigate the effect of
oxidation on chalcopyrite flotation. The results show that with hcrease in aeration tirne
there is a decrease in the flotation recovery. Chaicopyrite is siightly depressed by oxidation
because of the formation of cupric and femc hydroxides on its surface.
where chalcopyrite reacts directly with xanthate ions. Cuprous xanthate seems to be
responsible for the flotation of chalcopyrite at -460 m V vs. SCE. Since this reaction can
occur before the dixanthogen formation, there is no doubt that cuprous xanthate
participates in the hydrophobization of chaicopyrite. PAX adsorbs on chalcopyrite at the
reducing potentials, Le., at potentials below the formation potential for dixanthogen. The
floatability becomes hi& once the potential for dixanthogen formation is exceeded.
(EOz-159mV) (6.2.8.2)
6.3 Conclusions
characteristics of chalcopyrite under the same conditions. From the results obtained, the
following conclusions can be aated:
- The hydrophobie species responsible for hydrophobicity of chalcopyrite are both cuprous
xanthate and dixanthogen. Moderate flotation of chaicopyrite occurs prior to dixanthogen
formation, whereas strong flotation requires dixanihogen formation.
-A
- There
was a considerable decrease in flotation for high alkaiine media due to the
decomposition of dixanthogen.
SCE.
- The depression of chalcopyrite with sodium cyanide was show to be unstable. Xanthate
was initially removed fiom the chalcopyrite surface by cyanide but xanthate readsorbed
- Increase in sodium sulphide contact time increased the desorption of xanthate from the
surface of chalcopyrite.
CHAPTER 7
Cornparison of the FIotation Chemistry of Synthetic Enargite,
7.1 Introduction
Chalcopyrite and enargite are considered to be copper minerais. Due to its arsenic
content, enargite is frthennore considered as a troublesome contaminant. Chalcopyrite
and enargite often coexist in the same ore deposit and behave sidarly in flotation systerns
with xanthate coiiectors are n o m d y produced in the same concentrate. The
understanding the Merence in the flotation behaviour between these two minerals is
industrially important because enargite separation is required d u ~ gthe flotation
processing of copper sulphide minerais. To achieve this aim, a senes of investigations
were made in this research. Sumaries of various results have been given in the previous
chapters. To avoid the effect of irnpurities. the investigations were limited to simple
systerns involving pure minerals, xanthate, depressants and pH regulating agents. Synthetic
enargite was used because the natural enargite sample contained a fine dissemination of
irnpurities. However, additionai experiments using natural enargite were conducted to
compare with the results obtained for synthetic enargite. A cornparison of the adsorption,
notation and depression behaviour of these minerals is can-ied out in this chapter with the
objective of reachg a possible selective depression of enargite.
7.2 Adsorption
The adsorption of potassium amyi xanthate on synthetic enargite, natual enargite and
chalcopyrite as a firnction of time for a xanthate concentration of 20 mg/l at pH 9 is
presented in Figure 7.2a.
10 20 30 4 0 50 6 0 70 80 9 0 1 0 0 1 1 0 1 2 0
Adsorption Tirne ( m i n u t e s )
The results show that the xanthate adsorption on synthetic enargite in the initial 10
minutes is rapid and reaches a plateau at 60 minutes of contact. The xanthate adsorption
on the natural enargite suface exhibited a sirnilar pattern with two-thirds of the adsorption
density of synthetic enargite. The xanthate adsorption density on the chalcopyrite,
however, is only one-third that of synthetic enargite for 30 minutes contact. It takes about
two hours of contact to have sirnilar adsorption density for chaicopyrite and natural
enargite. One hour contact is found to be sufncient for both synthetic and naturai enargite
to reach equilibrium, while chaicopyrite requires more than one hour. The r d t s indicate
that the rate of adsorption for synthetic enargite is higher than that of natural enargite and
chalcopyrite at 20 mg/l xanthate concentration.
A significant dserence was observed between the behaviour of those minerais that form
dixanthogen predominantly and those that fonn metal xanthate. The latter reacts rnuch
more rapidly during an initial penod, whereas the former reacts at a rate that decreases
regulariy widi tirne. This phenornenon was also observed by Mison et al. (1972) for other
sulphide minerals.
Figure 7.2b shows the adsorption isotherms of potassium amyl xanthate on minerais
at pH 9. The adsorption isotherms are similar in shape and exhibit three different regions.
At low equilibrium concentrations, the adsorption density of xanthate on minerals rapidly
increases with the concentration. The subsequent plateau region demonstrates that the
adsorbed collector remains relatively constant. The final stage indicates that further
adsorption takes place, but at a much lower rate. According to the isotherm classification
al1 these isotherms belong to the L type curves. The first part of the curves follows
Freundlich type isotherms which can be represented by r = kcl'" and the second part gives
m g , the
adsorption density of synthetic enargite is lower than that of naturd enargite and
chdcopyrite.
....,.,.-.,..-....-.. . ..
-........*............
< . . .. . . . ,-..-.--..
. . , <.......
:--...--,
. ....
...............
-...-.-.... . . . .-.*.-.-*.*-.--..*.*..*
. . . ....
. . . . ........
...........
-.---.
.................
. . . . .-..--.. .
....
............
. .. ...
-...-...
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
... ...
. .----..--.---.-*--.-:.-.:--:.:.:-:::
. . . .. ... ..
. . . . . . . .......,,...,..,....,...
.
. . .. .. ... ... --..
.........
. . . . . . . .
. . .. . .......................
. . .
.
.
.
.
.......
. . ....
.
<............
.......".-"...:-..f<.?'---..-.... . .. . . . .
.. .............................
.. . . .. .. . ..
.. . . . '..'*-=
. . . .
. . . .. .. . .. .. .
J J J J J J J J J J J J J J J J J J J . . .
................ . . . .
- t -----.,
+-:-?l,
--.---lfC-.-_.*--
" - . - , . . i r - - . i - . c . . - . . - - . . * . . . . .
....
L.-*-
...C
O. 1
-'
- - #
.
.
.
.. .. .. .. .. .. .. ..
.. .. .. .. .. .. .. ..
.. .. .. .. .. .. .. ..
.
.
. . .. ... ....... ... ...
10
....
-.--*.
. .
-C- C h a t c o p y r i t e
. . . .
.. .. . . . ..
, . . ..
.. .... ....
.
.
.
...........
. . .... .. ..
.. . . . .. .. . . . ..
100
100
The adsorption isotherm for natural enargite is apparently affected by the high
percentage of pyrite impunty. Pure enargite did not contain iron whereas the natural
sarnple contained about 9 percent of this element, which forms pyrite type inclusions. The
hydrophobic species for pyrite is dixanthogen (Fuerstenau et al. 1968),.and therefore, the
formation of cuprous xanthate as the prinnpal hydrophobic species on the naturai enargite
surface does not preclude the possbility that both cuprous xanthate and dixanthogen may
be present together on its surface. Thus the adsorption of xanthate on natural enargite
produces cuprous and dixanthogen complexes. These hydrophobic species have dso been
observed on tennantite (a copper arsenic sulphide) which contained pyrite as an impurity
(Mielczarski et al. 1995).
The resuits of these investigations indicate the sir ni la ri^ of adsorption characteristics
of these sulphide minerals in the presence of xanthates. For selective flotation, therefore, a
7.2.1
The depression effect of sodium cyanide on the mineral surfaces pre-adsorbed with
xanthate at pH 9 is shown in Figure 7.2.1. In a 15 mgA sodium cyanide solution, a
maximum of 93.5 percent of xanthate is removed fiom the synthetic enargite surface
within 60 seconds of contact. But the adsorption density recovers to 27.6 percent of its
original value afler a further 20 minutes of contact.
The results for natural enargite show that a maximum of 41 percent of xanthate is
removed fiom the minerai surface within 120 seconds and the adsorption density recovers
to 65 percent of its original value within 20 minutes.
corresponds to 80 percent of its onginai vaiue. Mer this point an increase in adsorption
density is observedA cornparison of the results show that the rate of xanthate desorption by cyanide is
slower for chaicopyrite than for naturd and synthetic enargite under the same conditions
and the depression of enargite appears to be more stable.
..
I
1O
..
..
..
..
..
..
I
.-
15
..
20
Figure 7.2.1: The effen of cyanide contact tirne on the pre-adsorbed .wthate on
minerals at pH 9. 20 mg/l PAX and 15 mg/l NaCN concentration.
As can be seen from Table 7.1 the desorption of xanthate by sodium cynide from the
Table 7.1: The effea of depressants on the pre-adsortied xanthate on synthetic enargite.
naturai enargite and chalcopyrite.
Test Conditions
initial PAX Conc.=SO.O mgIl, Contact Tirne40 min., pH4.0
Adsorption Deasity mg/m2
F i-Conditioned With Coiiector. Then With Depressant
Original
%
NatS
NaCN
%
%
-01
10 mg/
15 mgiI
50 mg/i
3.991
0.707
1.897
17.72
47.53
0.849
21.27
Minerai
Synthetic
Enarate
Nahuai
Enargite
Chahpyrite
2.859
1.788
62.54
2.318
81.07
1.541
53.89
2.789
2.327
83.43
0.941
33.74
2.000
71.70
The data for 10 mutes of conditioning were obtained by interpolation nom the data for 5
and 20 minutes of conditioning.
conditioning the mineral sarnples in sodium cyanide solution followed by adsorption tests.
is given in Table 7.2. The adsorption density is 22.4%, 69.19% and 80.39% of the original
Table 7.2: T'he effect of depressants on the .uanthate adsorption on synthetic enargite.
natural enargite and chalcopyrite.
Test Conditions
Minerai
Onginai
3.99 1
Synthetic
Enargite
Naniral
2.859
Enargite
Chal~op~yite 2.789
NaCN
15 mgi
0.894
60.01
1.978
69-19
2.484
86.88
1.907
66.70
1.926
67.37
2.242
80.39
1.054
37.43
1.958
70.20
2.141
76.77
A cornparison of the resuits, presented in Tables 7.1 and 7.2, shows the effect of
sodium cyanide on the pre-adsorbed xanthate and on the surface of the minerai foliowed
by the xanthate addition.
The desorption of
solubiiity of cuprous xanthate in the cyanide solution and the fonnation of the complex
Cu(CN4)' as the predominant species. Cyanide or cyanide complexes may aiso be
adsorbed on the mineral surface. As for chalcopyrite, on the other hand, cyanide can react
with dixanthogen fomllng an -1
noted that the concentration of cyanide is critical and the excess amounts would result in
the depression of chaicopyrite. Cyanide ions also form extremely stable complex ions with
iron on the chalcopyrite surface. This complex accounts for the stronger effect on the
surface of chalcopyrite than on the pre-adsorbed xanthate.
The effect of sodium sulphide contact time on the pre-adsorbed xanthate is shown in
Figure 7.2.2. The results show that the desorption of xanthate fiom the surface of al1
three minerals happens continuously up to 20 minutes. The effea is the highest for
chalcopyrite and the lowest for natural enargite as presented in Table 7.1. As is evident
The adsorption densities are 86.9%, 68.0% and 37.4% of the original adsorption density
for natural enargite, synthetic enargite and chaicopyrite, respectively. These results also
show the order of increase in depression effm of sodium sulphide on minerais.
The sudace properties of synthetic enargite are modified by the chemisorption of the
suiphide ions and xanthate adsorption could not have occurred. Since the hydrophobie
species of synthetic enargite is aiprous xanthate and its formation could have occurred as
reduced potentials, then the mechanism of the sodium sulphide depression effect is not due
rnainly to its reducing property. On the other hand, the depression mechanism of sodium
sulphide on chaicopyrite is mainly due to its reducing property. This accounts for the
1O
15
2O
S o d i u m Sulphidc C o n t a c t T i m e ( m i n u t e s )
Figure 7.2.2: The effect of sodium suiphide contact time on the pre-adsorbed
mthate on minerals at pH 9.20 mgIl PAX concentration and
10 mgh sodium suiphide coqcentration.
7.2.3
Figure 7.2.3 shows the effect of permanganate on pre-adsorbed xanthate for synthetic
depression effect on synthetic enargite. Xanthate is essentidy removed fiom the synthetic
enargite surface in les than 60 seconds and readsorption of xanthate is very Iow even at
20 minutes contact. For natural enargite, xanthate is initidy removed fiom the mineral
surface foiiowed by readsorption up to 5 minutes and no significant change after that. This
effect is initidy the same for chaicopyrite but readsorption is increased to higher values
after 2 minutes. Table 7.1 shows that the depression of minerals by permanganate is in the
order of synthetic enargite > natural enargite > chaicopyrite.
-E
.4
c.
......................................
.
.
.
........
1O
+S y n t h c i i c E n a r g i i c
+Narural Enargiic
Chilcopyrite
15
..1...
.........
20
K M n O q C o n t a c t T i m e (m inutcs)
Figure 7.2.3: The effect of KMnOI contact time on the pre-adsorbed .xanthate on
minerals at pH 9. 20 mg/l PAX and 50 mg/l KMnOd concentration.
dixanthogen and hydrated forrns of reduced manganese oxides which cause variations on
the d a c e of minerais by increasing the spontaneous oxidation. The formation of
dixanthogen, however, weakens the depression effect of permanganate on chaicopyrite. As
described in earlier chapters the oxidizing power of permanganate exerts some action on
the surface of the minerd by producing difEerent hydrophilic forms of hydroxides on the
surface. The effect of permanganate on the surfaces of naturai enargite and chalcopyrite is
also due to the reducing action of the ferrous ion in the minerals, which results in the
formation of hydrated oxides of iron. The rate and degree of formation of these
hydrophilic species on the surfaces of minerais, although different. cause depression of
these minerals.
The relationship between pH and the adsorption density of xanthate for three minera1
samples is shown in Figure 7.2.4. The adsorption density for synthetic enargite remains
relatively high and constant from pH 6 to pH 9 and decreases at the higher pH values. The
sarne results are obtained for natural enargite in the range of pH 6 to pH 9 with
approximately one-third of the adsorption density of synthetic enargite. The associated
bigher than 9. The pH effect on the xanthate adsorption on chalcopyrite aiso started at pH
values above 9.
+Synthciic Enargitc
+Natural
Enargiie
-C- Chalcopyrirc
7.2.5
The effea of aeration on the xanthate adsorption density is presented in Tabie 7.2.
The adsorption densities after 20 minutes aeration were 60.0, 67.4 and 76.8 percent of the
original adsorption densities for synthetic enargite, naturai enargite and chalcopyrite,
7.3 Flotation
Figure 7.3 shows the flotation recovery of synthetic enargite, natural enargite and
chalcopyrite as a h d o n of xanthate concentration at pH 9.
1O
20
30
40
50
O r i g i n a l X a n t h a t c Concentration ( m g t i )
It is obvious that the relationship between the collenor arnount and the mineral
recovery is about the same for the three rninerals. The flotation recovery of dl three
minerals increases with xanthate concentration. The relationships tend to be parabolics
with higher increases at low concentrations and gradual asymptotic approach at higher
values of xanthate concentration. For synthetic enargite a maximum recovery of 78
percent is obtained at a 30 m@
concentration, the increase in the flotation recovery becomes gradual. The flotarion
recovery for natural enargite at 30 mgIl xanthate concentration is about 77 percent but
exhibit a higher increase in flotation recovery at PAX concentrations greater than 20 mg/l.
The recovery of chalcopyrite at 30 mg/l xamhate is 86 percent. Also, its recovery
increases at xanthate concentrations higher than 20 mg/l.
As these results show, the floatability of the three minerals up to about 33 mg/i
xanthate concentration are in the following order:
The effect of sodium cyanide contact time on the flotation recovery for the three
minerals is presented in Figure 7.3.1. Under standard conditions the recovery of synthetic
enargite decreases fiom 75 percent to about 14 percent at a contact tirne of one minute
and re-bounds to about 24 percent d e r 20 Nnutes which shows that the depression of
enargite is stable with time. The flotation recovery of natural enargite decreases to 23
percent at 2 minutes contact tirne and is about 33 percent at 20 minutes. For chalcopyrite,
the flotation recovery decreases to 35 percent afker 2 minutes contact with cyanide
solution. The recovery is 65.4 percent at 20 minutes which shows that the depression of
chalcopyrite is not stable with tirne. This indicates that enargite might be depressed and
partially separated fiom chaicop~teby cyanide afker a prolonged contact tirne. A
cornparison of results for 10 minutes conditioning time is presented in Table 7.3.
aC
N Contact Tim
e (minutes)
Figure 7.3.1: The effect of NaCN contact tirne on the floatabiIity of minerais at pH 9.
20 mg/i P A X and 15 mgA NaCN conenuations.
Table 7.3: The effect of depressants on the synthetic enargite. namral enargite
and chalcopyrite floatability.
Minerai
1
Synthetic
Enargite
Naturai
Enargite
Chalcopyite
Test Conditions
Initial PAX Conc.=20.0 mg,.Contact Tirne= 10 min.. pH=9.0
F i Conditioning Wih Xanthate. Then Adding Depressant
% Flotation Recovery
First
Conditioned
With Collecter, Then With Depressant
Original
NaCN
NazS
KMnOj
15 mgil
10 mgIl
50 mgii
74.95
20.23
51.17
38.82
71.25
28.44
55.97
42.75
80.65
47.16
22.22
51.82
The eEea of sodium cyanide on the flotation, evduated by conditioning the mineral
sarnples in 15 r
n
d sodium cyanide followed by adciing xanthate and flotation, shows that
the flotation recoveries decrease to 21.0, 47.8 and 56.6 percent for synthetic enargite,
Table 7.1: The &ect of depressants on the synthetic enargite. naturai enargite
and chaicopyrite floaability.
Test Conditions
pH=9.0
Origmi
Synthetic
Enargite
Naturai
Enargite
Chalcopyite
% notation Recatery
First Conditioned With Depressant Then With Coiiector
NaCN 1
NazS
KMnOd
1 Aeration
15 mg/l
10 mg/l
50 mg/l
20 min.
71.95
21.00
55.60
45.08
50.25
7 1.25
47.75
57.83
47.35
5 1.25
80.65
56.62
26.15
50.9 1
67.44
The effect of sodium sulphide on the flotation recovery is given in Figure 7.3.2. The
results show that the flotation recovery decreases continuously for al1 three minerais with
the greatest effect on chaicopyrite and the smallest effect on natural enargite. Table 7.3
shows the effect of 10 minutes conditioning in 10 mg/l sodium sulphide solution for
synthetic enargite, natural enargite and chalcopyrite pre-conditioned with xanthate.
Figure 7.3 -2: The efkct of sodium suiphide contact t h e on the floatability of minerais at pH 9.
20 mg/i PAX concentration and 10 mgA sodium suiphide concentmion.
The effect of sodium sulphide on the minerai surfaces was aiso investigated by
conditioning the mineral samples with Na2S followed by the xanthate addition and
flotation. The results show that the flotation recoveries are 55.60. 57.83 and 26.15 percent
for synthetic enargite, naturai enargite and chalcopyrite, respectively (Table 7.4).
Figure 7.3.3: The effm of pH on the floatability of rninerals at 20 mg/I PAX concentration.
At solution pHs higher than 9, the depression of natural enargite and chalcopyrite occurs
with stronger effect on chaicopyrite. At a pH higher than 10. the chalcopyrite flotation is
reduced from 80% to below 70%, and rapidiy decreased to below 30% at pH 12. The
greatest depression effect on both natural and synthetic enargite starts at pH 1 1.
The effect of pH on the floatability of rninerals may be explained in terms of the species
responsible for hydrophobicity. The flotation recovery of enargite, whose principal
hydrophobie species is the cuprous xanthate form, is iess affected by pH in the range of 6
to 11. This indicates the ease of formation of the metai xanthate on the surface fiom the
readily ionized xanthate.
[t
would appear that a slower formation rate and decreased nability of dixanthogen in the
more aikaline solutions is responsible for the drop in chalcopyrite recovery. Since
dixanthogen is the effective hydrophobic species for chaicopyrite. anything that would
decrease its effective concentration or rate of formation would decrease the floatability of
chaicopyrite.
From spectroscopie and electmchemical studies it has been established that pyrite
floats weU by xanthates mainiy due to the formation of dixanthogen on its surface
(Mielczarski et ai. 1995). Pyrite is a n-type mineral and its hydrophobic species is
dixanthogen. Therefore its notation recovery decreases with pH. Because natural enargite
contains high percentages of pyrite, the recovery of natural enargite was also dected and
decreased with pH.
effea on the pyrite flotation. Table 7.3 shows that there is no selectivity between the
floatabmty of minerais with KMn04.
+ Natural Enargite
-A-
Chalcopyritc
KM
no4 C o n c c n [ration
(rn g / l )
The effect of aeration on the flotation of the three minerals is presented in Figure
7.3S.The test results show that 2 hours aeration significantly decreases the recovery of
Table 7.4 represents the eEkt of 20 minutes aeration on the floatability of three
minerais. Conditioning with air resdts in the depression of ail three minerals, but the
floatability of both synthetic and naturai enargite is afkted to a much greater degree than
depression of chalcopyrite.
s y n t h c t i c Enrrgitc
+N a t u r d Enargitc
A
....
Chalcopyritc
A e r a t i o n T i m c (minutes)
Figure 7.3.5: The effect of aeration tirne the floatability of minerals at pH 9 and
20 mgIl PAX concenuation. .
Further investigation was conducted to explore the effect of pulp potential on the
floatability of synthetic and n a d enargite and chaicopyrite at pH 9. The results are
shown in Figure 7.3.6.Chalcopyrite may be floated preferentidy at more oxidizing
potentials, wMe synthetic and natural enargite may be floated preferentidy at more
reducing potentials. The anodic limts were controiied by adding potassium permanganate,
while sodium sulphide was used to control the cathodic limits. The floatability was poor in
either more oxidizing or more reducing potential ranges. The lower recovery at more
oxidizing potentiais is due to excessive oxidation of the mineral swface. Although slight
oxidation of these minerals is necessary for notation, excessive oxidation is detrimental.
Enargite was appreciably more active electrochernically than chdcopyrite. It was found
that because of its elearochemical activity enargite was oxidized more readily than
chaicopyrite by air. At more reducing potentials, the formation of dixanthogen may be
inhibited if pulp potentials in notation are below the rest potentiai of the X/Xt couple
which was calculated to be -164 m V vs. SCE.The formation of cuprous xanthate. on the
other hand. occurs a? potentiai ranges appreciably below this potentiai. The data presented
in Figure 7.3.6 suggest that the separation of enargite and chalcopyrite may be possible in
certain regions of pulp potential. At -250 mV, both synthetic and natural enargite could be
floated and chdcopyrite could be depressed. At +IO0 mV, chalcopyrite is fioated and
natural and synthetic enargite are depressed.
1
. N i t u r a l Enurgitc
-~.*'-----Y--'-"".**..-..--..-.--..ii.*-.~.-.-~~..
.-
Chalcopyritc
I
,600-500-400-300-200-1
O0 O
Potential (m V v s .
Fi-
7.3.6: Relationship between flotation recwery and pulp potentiaf for minerals
at pH 9 and 20 mg/l PAX concentration.
Larger scale tests were performed using a 250 g Denver flotation ce11 in order to
check the results obtained from the Hailirnond tube. In these tests pure silica sand, -200
mesh in size, was used as a gangue mineral. Two gram of the minerai to be tested were
mixed with silica sand for flotation. The conditions of flotation were kept the same for al1
tests and are listed in Table 7.5. Under these flotation conditions chalcopyrite gives the
highest recovery and naturd enargite the least. These results are in good agreement with
Concentrate. g
Head g
Conc. As Assay. %
Head As Assay. %
Conc. Fe Assay. %
Head Fe Assay. %
Conc. As Distribution, %
Conc. Fe Dimiution. %
Head Distribution %
Recovery. %
Chalcopyrite
250
Synthetic Enargite
Natural Enargite
250
2
9
20
20
2
1
250
2
9
20
20
2
1
1.67
252
17.52
O. IS
1.69
252
13.01
O. 12
28.7
0.24
77.40
72.71
100
76.99
100
72.80
2
9
20
20
7
1
&sui&
1.72
252
81-62
100
82.60
7.5 Conclusions
- The results of adsorption and flotation studies indicate the similarity of the adsorption
and fiotation characteristics of these sulphide minerals in the presence of xanthates. The
major difficulties are the separation of the mineras by the flotation method without
depressants.
- It was s h o w that the pulp potentials rneanired in the xanthate solution cohcide with the
redox potentiai of the xanthatddixanthogen couple. Eh has a controlling influence on the
notation of enargite and chalcopyrite. The proper control of pulp potential is expected to
provide an opportuNty for separating their mixtures by Merentiai flotation.
synthetic and naturai enargite than on chaicopyrite surface pre-conditioned with PAX.
Moreover, the effect is more significant on synthetic enargite than on natural enargite.
Sodium suiphide, on the other hand, has the strongest depression effect on chalcopyrite
and its effea on synthetic enargite is higher than on nanual enargite.
observed that sodium cyanide has a stronger depression effect on synthetic and naturai
enargite than on chaicopyrite. It has a higher eEect on synthetic enargite than on natural
enargite. Conversely, potassium permanganate has the least effect on chalcopyrite. Its
effect on the synthetic enargite surface is higher than on naniral enargite. Sodium sulphide.
on the other hand, has the greatest effect on chalcopyrite with the least effect on natural
enargite. The effect of aeration is of the same order as the effect of KMnOI on the
minerais.
- Depression of enargite by sodium cyanide is stable with time whereas the depression of
chalcopyrite is not stable with time. This indicates that enargite might be depressed and
- The general conclusion is that the highest sdsctivity is obtained by using sodium cyanide,
while less selectivity is achieved by sodium sulphide and no selectivity observed by
oxidation.
CHAPTER 8
Reduction of the Arsenic Content in Copper Concentrates
8.1 Introduction
copper concentrate containing up to 10% arsenic may be produced (Smith and Pardes
1988). The arsenic bearing concentrates cannot be smelted as-is because arsenic would
pollute the environment and contaminate the smelter products (Biswas and Davenpon
1994). Concentrates containing a high percentage of arsenic are penalized by many
smelters. The main reason that penalties are applied is the additional costs incurred by the
smelters to remove them from the refined metal in order to comply with international
standards. Smelters cm also attract extra environmentai control costs because of the
arsenic impunty.
Pyrometailugical and hydrometallurgicai processes provide a means of removing
form of an oxide (As203),h o w n in the trade as white arsenic. White arsenic is soluble in
water and
is quite toxic. Because of its solubility and toxicity, the disposal of the chernical,
where market for the oxide are lirnited, has caused considerab!e problems. In nonoxidative
techniques a possible way to solve the arsenic problem, although it has never been
practised cornrnercidy, would be to dispose of it as arsenic sulphide, which occurs in
nature as the minerals orpiment (AS&) and reaigar (As2S5).The arsenic suiphide is more
than one hundred times less soluble than the oxide (Kusik and Nadkami 1988).
Hydrometailurgical techniques for removing arsenic f?om copper concentrates are
alternatives to the pyromerallurgical techniques. These techniques are discussed in detail
by Nadkami and Kusik (1988). However, the tabiiity of waste materials produced fiom
removing arsenic by existing hydrometallurgical techniques will not meet the regdatory
requirements of the future for long term disposai (Robins 1988).
Based upon these concepts, it is necessary to h d an alternative to current processes.
It is in this regard that the present work was undertaken. Since the specific gravity of
8.2
Separation Fiotation
The appropriate conditions for the separafion of enargite and chaicopyrite were used.
These conditions gave the highest Merences in the floatability of enargite and
chabpyrite in the single mineral flotation. Therefore, they were used in the separation of
a mixture of minerais.
8.2.1
Experimentai Techniques
Synthetic enarpjte and pure chalcopyrite were used for al1 the tests and the microflotation method described earlier was used for this purpose. The sampie was conditioned
for 20 minutes with the coiiector soIution in the flotation ce11 and then with depressant for
a desired time period foiiowed by one minute of flotation. The sample used for the
Hallimond tube test was a 2 g artificial mixture: 0.5 g enargite and 1.5 g chalcopyrite. This
composition was chosen (4.75% As) because enargite containing concentrates from
copper mines often contain up to 10% arsenic. An aqueous solution of the required pH
value, collector and depressant were used for flotation (Table 8.1). Elemental chernical
aiialyses of the minerais (Table 3.2) showed that the enargite contained of 48.42% Cu.
19.02% As and 32.56% S and the chalcopyrite contained of 33.2% Cu, 29.9% Fe and
35.6% S. Since arsenic is only exist in enargite and iron is only exist in chalcopyrite, then
the recovery of enargite in the concentrate can be cdculated using the content of arsenic in
the concentrate (Le., the percentage of As in the concentrate), and the recovery of
chalcopyrite can be calculated using the content of Fe in the concentrate (Appendix A5).
Because the unwanted mineral is enargite, which is also a Cu-containuig mineral, the
loss of copper in the tailings is unavoidable. Theoreticaiiy, the CdAs weight ratio in
enargite is 2.54 and, therefore, 32.7% of the copper in the sarnple is contained in enargite.
8.2.2
Resuits
contact time the coppdarsenic separation efficiency was 13.93 percent, but the copper
recovery was very low. For 20 minutes contact time the copperfarsenic separation
efficiency was maximum and the copper recovery was 55.21 percent. The percentage of
arsenic in this test was dso minimum. The concentration of C N was criticai, and the
excess concentration of 20 m g resulted in chalcopyrite depression (i-e.,6 1% chalcopyrite
recovery).
Test results show that ushg lMr-01 as a depressant for enargite resulted in a
When sodium sulphide was used as the chalcopyrite depressor, the fioated product
contained high arsenic and the nodoated product contalied low arsenic. The results show
that copper/arsenic separation efficiency was 22.12 percent and 24.15 percent for NazS
efficiency or minimum arsenic grade of 3.30 percent could be obtained for 20 minutes
sodium sulphide contact tirne at a concentration of 10 mgl.
Table 8.1: Separation flotation tests for the mixture of enargite and chalcopyrite
at 4.75% As in feed sample.
* Non-floated Weight
8.2.3
Discussion
The arsenic problern in a copper concentrate could be alleviated by the optimkzation
arsenic grade of 2.75 percent was obtained at 15 mg/l NaCN concentration and pH 9 for
20 minutes contact time. With an increase in NaCN concentration to 20 mg/i a maximum
also very similar at these conditions. As well, the copper and arsenic recovenes are higher
using KMnOJ Using 15 mg1 sodium cyanide at pH 9 and 20 minutes contact time, or 10
mg/l sodium sulphide at pH 9 and 20 minutes contact time, gives very simiiar
coppedarsenic separation efficiencies. The arsenic rejection is higher in case for the use of
sodium cyanide but with a lower copper recovery.
Generally speaking, regression analysis of the data, presented in Figure 8.2.3. which
shows copper recovery versus arsenic recovery. indicates that the increase in arsenic
rejection brings about an increase in the rejection of copper.
% Arsenic Recovery
Figure 8.2.3: Copper recovery vernis anenic recovery at 4.75% As in feed ample.
Moreover. fiotation is a suitable method of reducing the arsenic content of the copper
concentrates by using sodium cyanide as an enargite depressor. This process consists cf
isolating chalcopyrite in a high-copper concentrate. It entails physical separation of the
chalcopyrite by Eoth flotation to fom a low-arsenic product and an arsenic-rich tailing.
The low-arsenic product is deained for smelting and the arsenic-rich product could be
discharged since it is a natural sulphide and less toxic ihan arsenic oxide which is produced
in pyrometallurgical processes, or could be used for hydrometallurgical extraction in which
economicdly feasible due to the lower mass quantity to process. Furthemore, because
chalcopyrite is a major mineral and enargite is a minor minerai, and therefore it is not
logicdy to depress chalcopyrite using sodium sulphide and float enargite (Tajadod and
Yen 1997a).
8.3 Conclusions
An attempt has been made to snidy the possibility of arsenic reduaion in a copper
concentrate containhg enargite. From the results obtained, the foilowing conclusions can
be stated:
- .A minimum copper recovery of 42.54 percent was attained by using 15 mg/i NaCN at a
contact time of 5 minutes. However, a copper recovery of 48.00 percent was obtained at
20 minutes contact time by 20 mg/l NaCN.
- .ksenic recovery was a minimum using 20 mg/l NaCN at a contact tirne of 20 minutes.
and the copper recovery was also a minimum.
- The minimum grade of arsenic was 2.18 percent. This is the best result regarding the
arsenic reduction in the copper concentrate for the test conditions in this study. This grade
corresponds to 48 percent copper recovery.
- The overall conclusion is that using sodium cyanide at a concentration of 20 mgll with a
contact time of 20 minutes gave the best results (the lest arsenic grade) for the separation
notation tests performed in this investigation.
9.1 Introduction
The renilts obtained in the previous chapters demonstrated that the selective flotation
has been previously studied (Tajadod and Yen 199%). Copper sites exist on the surfaces
of chalcopyrite and enargite, while arsenic sites exkt only on the surface of enargite.
Arsenic and its compounds are easily oxidized to arsenate. The ability of combining the
arsenate sites on the surface of enargite with MAA to form a strong hydrophilic layer of
magnesium ammonium arsenate. AsO&l&Mg.6H~O, is feasible. The adsorption of this
hydrophiiic film on the surface of enargite prevents the adsorption of xanthate.
Adsorption, flotation and surface tension techniques using MAA as a depressant were
employed to study the selective depression of enargite &om chdcopyrite. Synthetic
enargite and pure chalcopyrite were used for dl tests. However, additional expenments
were conducted with nanirai enargite. MAA was prepared by rnixing 0.5 mol rnagnesium
chloride, 2.0 mol ammonium chioride and 1.5 mol ammonium hydroxide.
Adsorption and flotation methods have been described earIier. For s d a c e tension
measurements, 0.5 grams of mineral were conditioned with MAA for 10 minutes, then
with xanthate for 20 minutes. The solution was then removed and flotation performed in
the water-methanol solution. A series of tests was also performed without conditioning the
minerais with MAA The d a c e tensions of the water-methanol solutions were
predetermined employing the du Nouy ring method with a Fisher Surface Tensiomat
Mode1 2 1. A platinum-indium wire ring was slowly puiied through the interface between
the two phases and the maximum force required to pull the ring out of the interface was
9.3 Results
9.3.1 Adsorption
enargite and chdcopyrite conditioned for 10 minutes with difKerent MAA concentrations
at pH 9 is presented in Figure 9.3. la. The results show that the xanthate adsorption
density on both natural and synthetic enargite decreases with an increase in MAA
concentration. The amount of the decrease is smaU for concentrations lower than 150 mg/i
MAA. As the concentration of MAA is exceeded 150 mgll the adsorption density
decreases rapidly. The adsorption density reaches the lowea point at 250 mgA MAA. At
250 mgll MAA concentration there were about 88 and 76 percent reductions in adsorption
By conditioning the synthetic and naturai enargite samples with MAA at pH 9, the
xanthate adsorption density decreased after 10 minutes retention tirne. M e r this tirne the
xanthate adsorption density stayed constant and no further xanthate re-adsorption was
observed (Table 9.1).
Table 9. i :The &ect of MAA conditioning time on the adsorption density of PAX on synthetic and
aatural enargite.
Test Conditions
MAA Concentration = 250.O mg/l, pH = 9.0
Conditioning
Tirne
(min.)
0.0
5.0
10.0
20.0
0.596
-
Enargite
0.833
-
Aeration. 10 min,
Synthetic
Enargite
0.471
Naturai
Enargile
0.602
However, the xanthate adsorption density increased with an increase in initial xanthate
concentration after conditioning the minera1 samples in a solution containing 250 mg/i
MAA. The increase in xanthate concentration from 20 to 30 mg/l increases the adsorption
densities to 22.1 and 18.7 percent for synthetic and natural enargite, respectively.
50
100
150
200
250
300
M A A Concentration ( m n / l )
Figure 9.3.l b shows the effea of pH on the xanthate adsorption density on the
minera1 surfaces. Initiaiiy, synthetic enargite, natural enargite and chaicopyrite were
conditioned with 250 mg/i MAA for 10 minutes followed by adding xanthate at 20 m g .
The results show that MAA has aimost no effect on the adsorption density of
chalcopyrite and rnarkedly inhibits the xanthate adsorption on enargite. In the pH range of
7 to 1 1 , the xanthate adsorption density on synthetic and natural enargite is low. The
and naturai enargite before conditionhg with MAA at pH 9. The results presented in
adsorbed with xanthate was aiso examined at pH 9. The redts indicate that the
adsorption densiy afler 10 minutes was 3.806, 2.705 and 2.698 mg/m2 for synthetic
enargite, natural enargite and chalcopyrite, respectively. The results reveal that the
application of MAA did not remove the xanthate &om the surface of the minerais.
9.3.2 notation
Figure 9.3.2a shows the relationship between MAA concentration and the flotation
recovery of synthetic enargite, naturai enargite and cMcopyrite at pH 9 d e r 10 minutes
of conditioning with MAA. The floatability of synthetic and natural enargite was affecteci
by increasing the MAA concentration. The flotation recoveries of both synthetic and
nanird enargite were below 15 percent at a 250 mgii MAA concentration. The flotation
recovery of chalcopyrite was not aEected by any MAA concentrations.
M A A C o n c e n t r a t i o n ( m g!l)
Figure 9.3.2b shows the effect of solution pH on the floatability of three minerais
following 10 minutes conditionhg with 250 m g MAA and floating with 20 mg/l
potassium amyl xanthate. The results showed that the recovery of synthetic and naturd
enargite at dl pH vaiues was in the range of 7-15 percent. The flotation recoveq of
chalcopyrite was 80-82 percent in the pH range of 7 to 9. As the pH increased fiom 9 to
11, the chalcopyrite recovery was reduced 60x11
80 percent to 47 percent.
1 O0
g0
)i
>
8 0 -...........
7 0 - ...............5 ...............
...............
The flotation behaviour of rninerals with the combined effect of aeration and MAA
was also studied. The results presented in Table 9.2 show a fbrther 2.34 percent decrease
in flotation recovery of synthetic and natural enargite. Again, there was a very small
mg11 the dEerence in chaicopyrite and enargite recovery is 7 1.16 and 65.87 percent for
chalcopyrite-synthetic enargite and chaicopyrite-naturai enargite, respectively. For 30 m g
PAX this difference is 74.27 and 69.48 percent, respectively.
Test Conditions
MAA Concentration = 250.0 mg/L Conditioning T e = 10 Min.. pH = 9.0
%R
9.24
14.53
Selectivity depends on the surface propemes of the solids to be separated. Solids may
be rendered hydrophilic (i. e., converted to high-surface energy solids) prior to flotation
through the selective adsorption of certain chernical reagents (i.e., depressants). It is also
possible, in accordance with the concept of the critical surface tension of wetting to
seleaively wet one inherently hydrophobie solid in preference to another by controlling
the surface tension of the flotation medium (Kelebek and Smith 1985). In this
investigation, an experimental program was undertaken to apply these concepts to the
separation of chalcopyrite and enargite, extending the conditions to a system where
hydrophobicity was induced by the collecter.
for separating enargite and chahpyrite. Figure 9.3.3a shows the relationship between
flotation recovery and sudace tension as regulated by rnethanol. The resuits show that the
dserence in flotation recovery for chalcopyrite-natural enargite is higher than for
chalcopyrite-synthetic enargite but still is not very much signincant for effective
separation. This is because, f i e r coilector adsorption. the wettability and notation
behaviour of enargite and chalcopyrite are sirnilar.
.......
+S y n t h c t i c E n a r g i t c
+Natural Enargitc
..........i..........._..........., ..........
.......
*-.--.,
".. ..
.......
..
......................
10
20
30
40
50
60
70
80
Surface T e n s i o n (d y n e s ~ c r n )
Figure 9.3.3a: The effect of surface tension regulated by methanol on the floatability of
minerals at pH 9 and 20 mgIl PAX concentration.
To enhance the separation efficiency in the flotation of chalcopyrite and enargite, the
cornbined effect of MAA and the surface tension regulation method was applied. The
chalcopyrite conditioned with 250 mgll MAA at pH 9. The results indicate that a good
flotation selectivity was obtained fiom about 53 to 70.5 dynedcm. The flotation recoveries
of chalcopyrite and enargite were 78-80 percent and 5-8 percent, respectively. The
results at 70.5 dynedcm corresponding to 1 percent vlv methanol gave the highest
selectivity. At methanol concentrations greater than 15 percent corresponding to 53.1
dyneskm, the chalcopyrite flotation was also suppressed.
10
20
30
40
50
60
70
80
Surface Tension ( d v n w c r n )
Figure 9.3.3b: The effect of surface tension nguiated by methanol on the fioatability
of minerals conditioned with MAA at pH 9 and 20 mgA PAX
concentration.
9.3.4
conditions were 30 m
and surface tension. The recovery of each mineral was calculated as descnbed in Appendix
A5 and the results are presented in Table 9.3.
Table 9.3: Separauon flotation tests for the mixture of enargite and chabpyrite
at 1.73% As in f d sample.
No.
Test Conditions
Depressant Depression Aeration
Time
250.0 mg/i
Time
(min.)
(-1
PAXConc.
(mm
pH
9
9
MAA
MAA
30.0
30.0
30.0
- 9
MAA
No.
Conc.
Methmol
FeedWeight
(%)
(8)
5.5
5.5
5.5
1O
10
10
10
Results
1
2
3
Wei@ (R)
4.20
,
4-10
4.17
%As
0.23
0.18
0.14
'
Yie
%Cu
Y&"
29.93
29.87
29.94
33.82
33.62
33.60
74.68
72.47
73.67
O/&
or
'ORh
10.17
7.77
6.15
O/&
84.10
81.92
83.5 1
%Sep. EE.
64.5 1
64.70
67.52
efficiency of 64.51 percent and a minimum arsenic grade of 0.23 percent was obtained.
The highest copper recovery (74.68%) was also attained in this case. M e r aeration for 10
minutes. the minerai urface was oxidized, and the arsenic grade was decreased to 0.18
percent. The copper recovery was also decreased to 72.47 percent. The application of 2
percent (vh) methand resulted to a M e r decrease of the arsenic grade to 0.14 percent.
In this test the separation efficiency and copper recovery increased to 67.52 percent and
73.67 percent, respectively.
9.4 Discussion
Because of the facility of oxidizability, As(0) and &(III) adsor oxygen from the pulp
and change to &o.Arsenic and its compounds are easiiy oxidized to the stable complex
potentiais, small ionic radius and high charges. Lorenzen et al. (1994) stated that when ptype arsenopyrite is oxidized by aenai oxygen or oxygen soluble in notation pulp, As(V) is
released in the form of arsenic acid and arsenates. On the other hand, according to
Nishimura et al. (1988) magnesiurn has a very high afnnity for arsenates and forms a very
strong hydrophii and insoluble compound of magnesium arsenate.
An examination of the atoms in the enargite crystal laaice (Figure 2.10.1b) shows that
arsenic atoms are situated at the apex, having the greatest number of unsanirated (free)
bonds and are therefore the mon active in oxidation. Atoms of copper and sulphur,
situated on the crystal edges, are less active (Glembotski 1972).
It was noted that MAA inhibits the attachent of xanthate to the enargite surface.
This is because of the relative ease of oxidizability of arsenic sites to the complex anion
[ASO~]"which possesses a great afiinity for MAq and they fom the strong hydrophilic
this compound is mongly hydrophilic which hinders the adsorption of xanthate on the
surface of enargite. Moreover, xanthate anions do not attach thernselves to minerais which
contain magnesium. In addition, the xanthate of rnagnesium is readily soluble in water
(Glembotski 1972).
The adsorption of MAA on the enargite surface appears to be more effective in the
absence of xanthate and it does not produce a depression effect in the presence of xanthate
adsorbed on the mineral surface. This is because the arsenic sites on the surface are
covered b y xanthate. When chaicopyrite was treated with M M solution, there were no
arsenic sites for MAA adsorption and no dpression effect for the chalcopyrite flotation.
In selective depression of enargite by the application of MAA or a combination of aeration
and MAA, the m&murn separation efficiency of 64.70 percent and a minimum arsenic
grade of 0.18 percent were obtained. The role of air oxidation couid be explained by the
oxidation of the enargite surface promoting the arsenate sites on the surface accessible for
W to fom magnesium ammonium arsenate.
The evidence of MAA adsorption on the enargite surface was conhned by infiared
spectroscopy. Figure 9.4 shows infiared spectroscopie results from the adsorption of
rnagnesium ammonium mixture onto the surface of synthetic enargite at pH 9. The
appearance of an adsorption band at 1450 cm-'in the spectra represents the ammonia
coordination complexes with metal ions (Little 1966), i-e. adsorbed ammonium ions. This
band is assigned to the bending mode of the adsorbed ammonium ions.
9.5 Conclusions
A new and effective depressant for enargite was developed using a mixture of
m).
- Flotation tests revealed that the recovery of synthetic and naturai enargite conditioned
with M&4 decreased to beiow 15 percent at al1 pH values between 7 and 11. Also,
chalcopyrite flotation was not affected by MAA from pH 7 to 9 and slightly decreased at
pH higher than 9.
- In selective depression of enargite a combination of aeration and MAA did not improve
the separation efficiency, but by the aeration effect the arsenic grade was reduced to 0.18
percent.
from 1.73 to 0.14 percent was attained by using a 2 percent (vh) solution of methanol.
- Conditioning with
would reduce 86.7. 89.6 and 91.9 percent of the arsenic in the ore, respectively.
CHAPTER 10
Summary, Conclusions and Recomrnendations for Future Study
For this study, initiaily, sodium cyanide, sodium sulphide and oxidation were selected
as possible depressants. The characteristics of this substances for selecrive flotation of
enargite and chalcopyrite were studied. The conventionai depressants. sodium cyanide and
potassium permanganate, are obviously appropriate for enargite depression. However,
used in large quantities, they also depress chalcopyrite. Alternately. sodium sulphide is an
effective depressant for chaicopyrite, but it also has some depression effect on enargite.
Again, because of environmental restrictions in the application of sodium cyanide. the
non-cyanide reagents would be more suitable for depressing enargite. With a rnixnire of
magnesium-ammonium as a depressant, enargite and chaicopyrite behaved differently. This
investigation demonstrated that a magnesium-ammonium mixture depressed enargite while
it did not have any depressing effect on chaicopyrite flotation.
It
is possible to use MAA to separate chalcopyrite and enargite using flotation process.
Detailed concIusions are made in the discussions and are listed at the end of each
chapter. A bnef summary of these conclusions is presemed as foliows:
Xanthate had a very high afFNty for synthetic enargite. The adsorption density was
was found to be
cuprous xanthate.
- The effect of pH on the adsorption density of xanthate started at pH values higher than
9
- The flotation of synthetic enargite was potential-dependent between -485 and '1
00 m V
vs. SCE.
Contact angle measurernents confinned that a maximum contact angle of 80.4" was
The addition of NaCN and KMnOd results in the desorption of xanthate from the
synthetic enargite surface. There was a decrease in synthetic enargite recovery by sodium
sulphide contact time. Synthetic enargite was also depressed by the application of air
oxidation. The effects of these depressants on synthetic enargite were in the order of:
sodium cyanide > potassium pemanganate > sodium sulphide
Aeration had airnost the sarne effect as potassium permanganate on the syntheric
enargite depression.
The results of adsorption and flotation studies indicated that a maximum recovery of
Sodium cyanide and potassium permanganate had a stronger depression effect than
- The adsorption density of xanthate on chalcopyrite was high. The hydrophobie entities
responsible for the hydrophobicity of chalcopyrite are both cuprous xanthate and
dixanthogen.
There was a considerable decrease in chalcopyrite flotation in high alkaline media due
- The flotation of chaicopyrite was potentid-dependent between -462 and +286 m V vs.
SCE.
The depression of chalcopyrite with sodium cyanide was shown to be unstable with
tirne. With an increase in sodium suiphide contact time there was an hcrease in the
desorption of xanthate from the surface of chalcopyrite. Potasaum permanganate had the
The results of the adsorption and the flotation midies indicate the similarities of the
adsorption and the flotation characteristics of these sulphide rninerals in the presence of
xanthates.
It .was shown that Eh has a controllhg influence on the flotation of enargite and
chalcopyrite. The difference in their flotation response to pulp potentid control provides
The depression effect of reagents on minerals under the same conditions is in the
foliowing order:
For sodium cyanide; synthetic enargite > natural enargite > chalcopyrite.
For sodium sulphide: chalcopyrite > synthetic enargite > natural enargite.
For potassium permanganate; synthetic enargite > natural enargite > chalcopyrite.
For aeration (air oxidation); synthetic enargite > natural enargite >chalcopyrite.
On the basis of the results the highest selectivity was obtained with sodium cyanide.
while less selectivity was achieved with sodium sulphide and no selectivify was observed
with oxidation.
By using sodium cyanide, potassium permanganate and aeration the reduction in the
A new and effective method for depressing enargite was developed by the application
The control of surface tension by adjusting the flotation medium with methanol
Several recommendations for fiiture research in t h fieid can be made. These include:
reactions of enargite could be hidied using cyclic voltammetry at dif5erent pH values with
and without the addition of depressants. The results may help idem*
the oxidation
The results summarized in the previous section were obtained only when the coliector
and depressants were present with no fiother added. The CO-adsorptionof xanthate and
fiother molecules rnay cause dserences in the behaviour of chalcopyrite and enargite
notation and depression. Funher work on this system is suggested for future study.
potentids can be controlled either through the use of redox reagents or through the
application of potentials fiom an extemal source. The application of redox reagents was
employed in the present research. Separation of a chalcopyrite-enargite mixture by
extemal potential control is also proposed for future work.
As zinc. cobalt and strontium also have high affinity for arsenates and produce strong
hydrophilic arsenate compounds, application of these ions for the depression of enargite
and other arsenic suiphide minerals is recornmended for future research.
REFERENCES
Ackemian, P.K.,Harris, G.H., Klimple, KR and Aplan, F.F.; Evaluation of flotation
collectors for copper sulphides and pyrite, 1. Common nilfhydryl collectors, IntemationaI
J m m u I of Mineral ProcesFing, 21. 1987. pp. 105-127.
Allison S.A. Goold, L.A., Nicol, M.J., and Granville, A; A determination of the products
of reaction between various sulphide rninerals and aqueous xanthate solution, and a
correlation of the produas with electrode rest potentials, Met. T m . . Vol. 3. 1972. pp.
2613-18.
Clifford, R K.. Purdy, K.L.and Miller, ID.; Characterization of sulphide minera1 surfaces
in fkoth flotation systems using electron spectroscopy for chemicai analysis, AIChE
symposmm. Vol. 71. No. 150, 1975. pp. 138-147.
Cook, M A , Nion, J-C.; Theory of water repeiient films on solids formed by adsorption
from aqueous solutions of heteropolar compounds, J. Phys. md Cd. C'hem-. 54. 1950.
pp. 445-459.
Craig, J.R., Vaughan, D.J.;Ore microscopy and ore petrography, John wley & Sons,
1981.
Crozier, RD.; Flotation: Theory, Reagents and Ore Testing, Pergamon Press, 1992.
Cullity, B.D.;
Elements of x-ray dif]Eiaction,Second Edition, 1976.
de Bruyn, P.L.,Agar, GE.;Surface chemistry of flotation; 1n:Froth Flotation, Fuerstenau,
D.W.. Editor, AIME, 1962, pp. 91-138.
Finkelstein, N.F., Allison, S . k , Lovell, V.M. and Stewart, B.V.; Naniral and induced
hyrdophobicity in suiphide mineral systems, AICM symposium Sertes. Vol. 71. No. IjO,
1975, pp. 165-175.
Finkelstein, N.P., Poling, G.W.; The role of dithiolates in the flotation of sulphide
rninerals, Minerals Sci. Engng , Vol. 9,No. 4. 1977. pp 177- 197.
Fuerstenau, D.W., Raghavan, S.; Sorne Aspects of Thermodynarnics of Flotation, In:
Flotation, A.M. Gaudin Memonal Volume, Volume 1, Editor M.C. Fuerstenau, 1976, pp.
21-65.
Fuerstenau, D.W.; Therrnodynamics of surfaces, adsorption and wetting; In: Pnnciples of
Flotation, Edited by R.P. King, 1982, pp. 3 1-52.
Fuerstenau M C , Kuhn M C and Eligillani D.A.; The role of dixanthogen in xanthate
flotation of pyrite, Tram AME. 241, 1968. pp. 148-156.
Fuerstenau, M C , Huiatt, J.L.and Kuhn, M.C.; Dithiophosphate vs. xanthate flotation of
chalcocite and pyrite, T r m . M E , No. 250, 1971. pp. 227-23 1.
Fuerstenau, M.C., Miller, J.D. and Kuhn, M C ; Chemistry of Flotation, Published by
SM.. 1985.
Fuerstenau, M C , Natalie, C.A. and Rowe, R.M.; Xanthate adsorption on selected
sulphides in the virtual absence and presence of oxygen, Part 1, Iw. Jour. Min. Process..
29, 1990, pp. 89-98.
Gajam, S.. Raghavan, S.; A kinetic snidy of enargite dissolution in ammoniacal solutions.
Int. Jour. Min. Proc.. 10. 1983. pp. 113-129.
Gaudin, AM., Schuhmann, R, Ir.; The action of potassium n-arnyl xanthate on calcocite.
Jour& of Physical Chemisby. Vol. 4, 1936. pp. 257-275.
Gaudin, A.M., Preller, G.S.; Adsorption of ethyl xanthate on galena, Trms AIME, Fol.
169. 1946. pp. 248-258.
Gaudin, AM., de Bniyh P.L. and Meiigren, O.; Adsorption of ethyl xanthate on pyrite,
Tram. AhW. 205, Jrm. 1956. pp. 65-70.
Gaudin, A.M.; Flotation, McGraw-Hill, New York, N.Y ., 1957.
Glembotski, V.A; Flotation, Primary Sources, New York 1963.
Guongming, L., Hongen, 2.; The chernical principles of flotation, activation and
depression of menopyrite, In: Processing of Complex Ores, Edited by G.S. Dobby and
S R . Rao. 1989, pp. 6 1-70.
Nakazawa, H., Iwasaki, 1.; Flotation behaviour of nickel arsenide, International Journal
of Mznerd Processing, 18, 1986, pp. 191-202.
Nishimura, T., Itoh, C.T. and Tozawa, K.; Stabilities of metai arsenites and arsenates in
water and eEect of sulphate and carbonate ions on their soiubiiities; Proceedings of the
symposium on Arsenic Metaiiurgy: Fundamentais and Applications, Phoenix, Arizona, Tne
Metallurgical Society, Inc., AIME,Pennsylvania, U S 4 Jan. 1988, pp. 77-98.
Osipow, L.I.; Sudace Chemiary: Theory and Industrial Applications, 1977.
Pang Jing; OBdation and wettabiiity of chalcopyrite and pyrite in alkaline solutions, Ph.D.
hesis, The Pennsylvania State university, 199 1.
Perez-Segura, E., Zendejas-Mendivil, S.; Arsenic in ore and concentrates of the Cananea
copper deposit, SII<IE T m s . Vol. 290, 1991, pp. 1922-1926.
Plaksin, I.N.; Study of superficial Iayers of flotation reagents on minerals and the influence
of the stmcture of rninerals on their interaction with reagents; International Mineral
Processing Congress, MM, London, 1960, pp. 253-268.
Poling, G.W.; Infiared studies of adsorbed xanthates, Ph.D. Thesis, The University of
Aiberta, 1963.
Poling, G.W.; Reaction between thiol reagents and sulphide rninerals. In: Flotation. A.M.
Gaudin Mernorial Volume, Vol. 1, M.C. Fuerstenau (Editor), AIME, New York, 1976,
pp. 334-363.
Rarndohr. P.; The ore minerais and their intergrowth. Pergarnon Press. New York, 1980
Richardson. P.E., Walker, G.W.; The flotation of chalcocite, b'ornite, chalcopyrite and
pyrite in an electrochemical cell. XVth Int. Miner. Process. Congr.. Cannes, Tome II.
1985, pp. 198-210.
Rineili, G., Marabini, A.M. and Alesse, V-; Depressing action of permanganate on pwte
and galena flotation, Complex Suiphide Ores Conference, Organized by MM, Rome,
M y , 1980,pp. 199-206.
Robhs. RG.; Arsenic hydrometdurgy; Proceedings of the symposium on Arsenic
Metdurgy: Fundamentals and Applications, Phoenix, Arizona, The Metailurgical Society,
Inc., AIME, Pemsylvania, US4 Jan., 1988, pp. 2 15-247.
Rogers, J.; Principles of sulphide mineral flotarion, Froth Flotation, 5 0 ~Anniversary
Volume, 1976, pp. 139-167.
Roos, J.R., Celis, J.P.and Sudarsono, A. S.; Electrochemical control of rnetallic copper
and chalcopynte-xanthate notation, Int. J. Miner. Process., 28, 1990. pp. 23 1-245.
Schulz, N.F.; Separation Efficiency, Tms.A M , Vol. 217,1970. pp. 81-87.
Shuey. R. T.; Semiconducting ore rninerals, Elsevier. 1975.
Smith, E.H.. Paredes, E.; How ST. JOE Gold's EL MD10 Mine has become a major
producer of high quality crude arsenic tnoxide, Proceeding of the symposium on Arsenic
Metallurgy: Fundamentals and ~ ~ ~ l i c a t i oPhoenix,
ns,
Arizona, The Metallurgical Society,
Inc., Pennsylvania, US4 Jan. 1988, pp. 145-160.
Somasundaran, P.; Interfaciai chemistry of particulate flotation, HChE Symposium Series.
Vol. 71. No. 150, 1975. pp. 1-14.
Somasundaran. P.. Sivakumar, A.; Advances in understanding flotation mechanisrns.
,Wnerals and Metallzrrgr cal Processing. 1988. p p. 97- 103.
Sutherland K.L., Wark LW.; Principles of Flotation. Melbourne, Australian Institute of
Mining and Metallurgy, 1955.
Taggart, A.F.. del Giudice, G.R.M. and Ziehl, O.A.; The case for the chernical theory of
flotation, Trms. M,112. Mmng Metho& 1934. pp. 348-38 1.
Tajadod, J., Yen, W.T.; A cornparison of surface properties and flotation characteristics of
enargite and chalcopyrite, accepted for XX International Mineral Processing Congress,
Aachen, Gemany, Sept. 2 1-26, 1997(a).
Tajadod, I., Yen, W.T.; Arsenic content reduction in copper concentrates, accepted for
the 36th Annual Conference of Metallurgists of C M , Sudbury, Ont.,Canada, Aug. 17-20,
1997(b).
Tipman, N.R.; The reactions of potassium ethyl xanthate in aqueous solution. Ph-D.
Thesis. The University of British Columbia, 1970.
Appendix A l
X-rays are produced when any elecnically charged particle of sutncient kinetic energy
is rapidly decelerated. Electrons are usuaiiy used for this purpose, with the radiation being
produced in an x-ray tube which contains a source of electrons and two metai electrodes.
The high voltage maintained across these electrodes rapidly draws the electrons to the
target, which they arike with very high velocity. Most of the kinetic energy of the
electrons striking the target is converted into heat with less than 1 percent being
transformed into x-rays.
The rays coming from the target consist of a mixture of Merent wavelengths and the
variation of intensity with wavelength depends on the tube voltage. When the applied
voltage is below a certain cntical value, the intensity is zero up to a short-waveiength
limit, then increases rapidly to a maximum and then demeases, with no sharp limit on the
long wavelength side. The radiation represented by such curves is called "heterochromatic
continuous" or white", since it is made up, like white light, of rays of many wavelengths.
When the voltage on an x-ray tube is raised above a certain critical value, which is
If one of the electrons bombarding the target has sufficient kinetic energy, it can knock an
electron out of the K shell, leaving the atom in an excited, high-energy state. One of the
outer electrons immediately fdls into the vacancy in the K shell, emitting energy in the
process, and the atom is once again in its normal energy state. The energy emitted is in the
There are severai lines in the K set, but only the three strongest are observed in nomal
dEaction work. K, (including Li and &) and & lines result nom the filling of a Kshell vacancy by an electron fiom the L or M shells, respectively. Although L ' s
wavelength is longer than Kp's , howwer, it is more probable that a K-shell vacancy will
be filled by an L eletmon than by an M electron, and thus the K, line is stronger than the
Kpline.
Many x-ray difEaction experiments require radiation which is as closely
monochromatic as possible. However, the beam nom an x-ray tube operated at a voltage
above the K excitation voltage contains not only the trong K, line but also the weaker Ko
line and the continuous spectmm. The intensity of these undesirable compounds can be
decreased relative to the intensity of the K, line by passing the beam through a filter made
of a material whose K absorption edge lies between the K, and Kp wavelength of the
target metal.
The backbone ui x-ray deaction is Bragg's law. Experimentally, Bragg's law can be
applied in two ways. By using x-rays of known wavelength 7\. and rneasuring 8. we can
detemine the spacing d of various planes in a crystd (stmcture analysis). Aiternatively,
we c m use a crystal with planes of known spacing d, rneasure 8, and thus determine the
wavelength
The angle between the diaacted beam and the transmitted beam is dways 28, which is
known as the difiaction angle, and it is this angle, rather than 8, which is usually
measured experimentaily. With known A. and measured 8. the spacing of various sets of
planes in the crystal structure c m be caiculated.
A Rigaku Rotaflex mode1 RU-2OOB Rotary Anode X-ray DifEactometer was used to
verifjr the purity of the synthetic enargite sample. Cr K, radiation (Chromium Anode, )c
2.29092) was produced to study the sample. Figure A l shows the difiaction angle vs.
intensity graph. The crystal structure of enargite is orthorhombic, the value of the distance
between adjacent planes (d) in the set (hkl) is (Cullity 1976):
1/d2= h2/a2+ k21b2+ 12/c2
By applying the above equation, the spacing for different planes can be calculated. Every
peak in the dfiaction angle vs. intensity graph represents a kind of system sati*ng
the
Bragg's law. The spacing of certain specified planes in the synthetic enargite lattice c m be
caiculated by applying Bragg's Iaw (1= 2.29092). By matching the spacing derived from
different ways, the planes incurring resultant peaks were found.
Appendix A2
Appendis A3
V = volume adsorbed
If a plot of P/[V(P,-P)] against PD. is made then a straight line should be obtained having
a siope of [(C- l)P]/[V,C] and intercept of l/p,,,C]
Linearity is generaily obtained in the relative pressure range of 0.05 to 0.35.The location
of the linear portion depends on the value of C. for example, when C = 100 the monolayer
point occurs at a relative pressure of about 0.1 and when C = 1 a monolayer is reached at
a relative pressure of 0.5.
Mixtures of helium and nitrogen are passed through a small U-shaped ce11 containing
the sample. At liquid nitrogen temperature, helium will not adsorb on any surface while
Ntrogen will physically adsorb on al1 substances. The amount of nitrogen adsorbed at
various partial pressures cm then be used to calculate the sarnple surface area and pore
structure.
Appendix A4
Calculation of Monolayer for Synthetic and Natural Enargite and Chalcopyrite
10-I6 cm2
10"
x 10''~x 6.023
'OI
x202000=0.671 mg/g
x 10"~x6.023x
10-'~x6.023
w 1 on)
Appendk A5
The percentage of Cu contributed by enargite in the artificial mixture is: 0.242/2 x 100 =
12.1
The percentage of Cu contributed by chalcopyrite in the artificid mixture is: 0.498/2 x 100
= 24.9
weight of
concentratd0.449
- Recovery of enargite
= 100 x percentage
of As in the concentrate
weight of the
concentrate10.095
0.498Iweight of concentrate
29.9 = 1.495 g Fe
100 =
4.4
= 100 x percentage
of Fe in the concentrate
weight of
concentrate/ 1.495
weight of the
concentrate/0.095
I .Wweight of concentrate
- %Cu
concentrate
Appendix A6
One hundred gram of ragent grade potassium arnyi xanthate were purified in three
immediately successive batches using the following procedure:
1- Dissolve xanthate in 250 ml of acetone, agitate by a magnetic stirrer.
xanthate.
7- Repeat procedures 4. 5 and 6 one more time.
8- Filter out the filtrate washing well with petroleum ether.
9- Break the filter cake into easily handied particles using the knife-edge of a spanila.
10- Store the filter cake in a vacuum desiccator containing a beaker of sulphunc acid and a
Appendix A7
where
cases less sensitive resonance Iines may be used if it is desired to extend the andyticd
The width of the resonance h e is inherentiy very s r n a being of the order of 10" nm.
Even when broadening due to various factors is considered, the width is nill only of the
order of 0.00 1 m. Thus, if a continuous source of radiation were used to measure atomic
absorption, a spectral slit width of about 0.0005 nrn would be required. Such resolution is
beyond the scope of most spectrographs and monochromaton.
Appendix A8
Method of Sulphur Anaiysis
AU molecules, with the exception of dipolar species nich as N2, H2,and OZ,absorb in
the infiared region. Because no ~o
s p e m r n is produced. Since al1 molecules have a characteristic spectrum, then the identity
and quantity of a compound can be determined. In the idiared detector ceil, energy is
emitted from a nichrome wire heated to 850C.Radiant energy, chopped at 85 & enters
the cell through a calcium fluoride window and is projeaed through the ce11 measuring
chamber which contains carrier or sarnple gases. Gases absorb irifiared energy as they pas
through the celi chamber, producing a spectrum. As energy exits the cell chamber through
cone and ont0 their respector. Each detector responds to the energy changes between the
carrier gas and the sarnple gas to ultimately determine the concentration of carbon and
sulphur. The detector output, AC coupled to the preamp, is amplified, rectified and
filtered. The analog voltage is converted to a digital signal through the A/D card and the
nominal energy when read at the ce11 output results in a voltage of 8.500 VDC.
Pnor to the beginning of an anaiysis. baseline is established by the computer. As the
andysis begins, the ce11 output decreases proponionally with the arnount of carbon (as
CO*)and sulphur (as S02) present in the IR cells. The computer reads ce11 output nine
tirnes per second. Each reading is converted to an equivalent mass per second by an
interval linearization equation. The results, corrected by calibration and compensated for
sarnple weight, are the total weight percentage of carbon and sulphur. An optional
moisture compensation can dso be applied to correct the result for dry bais reponing.
Appendix A9
Tabulatioa of Experirnental Results
Table 4. I. la
Adsorption Of Potassium Amvi Xanthate On S ~ t h e t i cEnargite As A Function Of Time
Test Conditions
Sample weight = 0.5000 g, Solution pH = 9.0(Adjusted with NaOH)
Bottle volume = 53.O mi. Agitated at 30 r.p.rn. and CentRtiiged for 30 seconds
Initial 'canthate concentration = 10.0 m@ = 0.530 mg
Test 1 Adsorption 1. Aiiquot 1 Chan Value 1 mg in 1
mg
1 Adsorption Densiry
Test ( Adsorption
No. 1 Tirne (min.)
Tesi
1
2
3
4
1
1
Adsorption
5-0
5
6
Test
No.
10.0
15.0
30.0
60.0
120.0
Adsorption
Tirne (min.)
1
*
ma
&
.
.
&
6b
(mu)
1
2
3
1
5.0
10.0
60.0
120.0
4/25
4/25
4/25
4/25
5.07
4.85
4-69
4.51
31.70
30.32
29.32
28.20
1.680
1.607
1.554
1.494
0.971
1.043
1.097
1.156
mg/g
1.941
2.087
2.193
2.312
mg/m3.889
4.181
4.394
4.632
Table 41.1b
Equilibrium Adsorption Of PAX On S_yatheticEname
..
Test Conditions
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bottle volume = 53.0 mi. Agimted at 30 r.p.m. and Centnfuged for 30 seconds
Initiai Conditions
mg in Solution
Test
Xanthate
Aiiquot
Chart Value Concentration
No. Concentration
(mgm
(mm
mm
1
2
3
4
5
6
Straight
10
20
30
50
100
20/100
20/100
10/100
AIiquot
i
1
2
3
Straight
.
..
&
.
4
5
1.330
0.774
0,214
0.485
0.581
Chart
VaIue
0.254
0.535
1.O60
1.590
2.677
5.247
F i Conditions
EquiIibrium
mg in
SoIution
Concentration
(mg(i)
mm
0.47
0.7 1
1.22
8.82
0.47
0.71
1.22
8.82
1.259
0.795
0.265
4.79
10.10
20.00
30.00
50.50
99.00
4.79
10.10
20.00
6.00 10.10
9.90
3.80
2.40
0.80
0.229
0.497
0.996
1.123
0.025
0.038
0.064
0.467
4/25
4/25
4/25
Adsorption Densin.
mg
Adsorbeci
23.75
15.00
5 .O0
m@g
mgm-
0.458
0,996
1.992
2.246
0.9 18
1.995
3.99 1
4.500
0.071
4.021
-0.051
2.916
2.895
2.844
5.843
5.800
5.698
Table 4.1.1.1
The Effest Of Sodium Cyanide Concentration And C o n M T m e On The PmAdmrbed XPnthate
1
Test
No.
1
2
3
4
initiai Xanfhate Concentration = 20.0 mgil = 1.060 mg &pH = 9.0 Modifieci Wih NaOH
NaCN
Contact
Finai Xantbate
Adsorption
Adsorption Density
mg
Conc.
Time
Conntration
Xanthate
<mg>
in Solution
(mfl)
(min-)
(mR/1)
mg(rn2
mMg
15.0
15.0
15.0
15.0
0.0
0-5
1.O
2.0
5.0
0.064
0.749
0.996
0.949
0.933
1.22
14.14
18.79
17.91
17-60
0.996
0.3 11
0.064
0.111
1.992
0.622
O.128
0.222
0.254
O. 127
3.991
1.246
0.257
0.445
0.509
Table 4.1.1. Ib
(mm
1
1O
20
Aliquot
Straight
u
-
Chart Value
(me/i)
10.00
20.00
10.00
20.00
Final Conditions
Equilibrium
mg in
Solution
Conc. (rngii)
0.530
1.O60
mg
Adsorbed
Adsorption
Densint
Table 4.1.1.2
[ The Effect Of Sodium SuIphide Concentration And Contact Time On The Pre-Adsorbed
Xanthate On S ~ t h e t i cEnargite
Initial Xanthate Concentration = 20.0 mgil = 1.060 mg & pH = 9.0 Modifieci With NaOH
Test
Na2S
Contact Fimi Xanthate
Adsorption Densiry
Adsorption
mg
No.
Conc.
Time
Concentration Xanthate
(mg)
(min,)
(mR/1)
e
(mm
in Solution
1
1
1
1
(ma)
1
1O
20
Straight
Aiiquot
Chart Value
(mCI/1)
.
b
10.00
10.00
20.00
20.00
Finai Conditions
Equilibrium
mg in
Conc. (mgii)
Solution
0.530
1.060
mg
Adsored
Adsorption
Densi@
mg/g
rngim'
0.658
1.3 18
1.356 2.716
-9
Straight
LI
3.80
7.21
3.80
7.2 1
0.201
0.382
0.329
0.678
Table 4.1.1.3
The Effect Of KMnOI Concentration And Contact Time On The Pre-Adsorbed Xanthate
On Syuthetic Enargiae
Initial Xanthate Concentration = 20.0 rnM= 1.O60mg & ?H= 9.0 Modifiai With NaOH
Test
KMnOj
Contact
Final
Adsorption
Adsorption Density
mg
No.
Conc.
The
Xanthate
Xanthate
(mg)
Concentration in Solution
(ma)
(min.)
(mm
Table 4.1.1.3b
The Effect Of KMnO, On Adsorption Density Of PAX On Synthetic Enamte
Test Conditions
KMnOJ Concentration = 50.0 ru@, Conditioning Tirne=1O min.
Sample weight = 0.5000g, Soluuon pH = 9.0 (Adjusted with NaOH), Adsorption time = 60 min.
Bode volume = 53.0 mi. Agitateci at 30 r.p.m. and Centrifugeci for 30 seconds
Initial Conditions
Test
Xanthate
Aliquot
Chart Value Concentration
mg in Solution
No. Concentration
(mgm
(W/l)
mm
10
20
Straight
Aliquot
Chart Value
Straight
*
$4
(wu
4.46
9.29
I0.00
10.00
20.00
20.00
Final Conditions
Equilibrium
mg in
Conc. (mM)
Solution
3.46
9.29
0.237
0.492
0.530
1 .O60
mg
Adsorbed
0.294
0.568
Adsorption
Density
rngimmgig
0.587
1.135
1.176
2.275
Table 4.1.1.4
The Effec Of CuSO, Concentration On Adsorption Density Of PAX On Synthetic Enargite
Test Conditions
Conditionhg Tirne= 1O min.
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption tirne = 60 min.
Bottle volume = 53.0 ml. Agitateci at 30 r.p.iu and Centrifugeci for 30 seconds
Initial Conditions
Xanthare
Aliquot
Test
Chart Value Concenuation
mg in Solution
No. Concentration
(mgm
fmgfl)
(mm
1
2
3
4
5
10
20
50
Straifit
AIiquot
1
2
3
4
5
Suaight
1
2
3
Straight
4
5
4.80
9.70
20.00
10.00
20.00
50.00
Chart Vaiue
Equilibrium
(MU
Conc. (rng/l)
mg in
Solution
0.11
0.24
0.36
2.82
3-80
4/25
4/50
.
6
4/25
4/50
9.70
20/100
6.
4.80
0.41
0.45
1.17
4.15
5.29
0.254
0.5 14
1.060
2.650
Adsoibed
~ d s otion
r~
Density
mg/g 1 rne/m-
0.249
0.50 1
1.042
1.716
2.783
0.497
0.996
2.009
1.003
4.174
2.083
6.874
3.431
5.565 111.150
0.232
0.490
0.998
1.275
1.795
0.464
0.980
1.996
2.550
3.j91
mg
0.931
1.963
3,999
5.110
7. <95
Table J.l.l.5a
Test
No.
mm
Solution pH = 1 1.0
50
LOO
20/100
10/100
Aliquot
Chart Value
Straight
2
3
..
4/25
4/50
Straipht
2
3
(ma)
0.39
0.70
1.14
4.06
5.70
2.677
5.353
50.50
i0.10
- 101.00
10.10
Final Conditions
mg in
Equilibrium
Solution
Conc. (mgfi)
Adsorbai
Solution pH = 7.0
0.021
0.39
0.037
0.70
1.14
0.060
1.345
25.38
3.776
71.25
0.239
0.493
1.000
1.279
1.471
0.478
0.986
2.000
2.558
2.942
0.958
1.976
4.007
5.125
5.895
0.196
0.470
0.891
0.392
0.941
1.781
0.785
mg
Adsorption
Densi-
Solution pH = 1 1.O
1.10
1.23
3.21
1.10
1.23
3.21
0.058
0.065
O. 170
1.385
3.568
Table 41.1 S b
The Effect Of pH On Adsorption Density Of PAX On Swthetic Enargite
Test Conditions
SampIe weight = 0.5000 g, pH Adjusteci with NaOH Adsorption Ume = 60 min.
Bottle volume = 53.0 ml, Agitateci at 30 r.p.m. and Centrifiiged for 30 seconds
Adsorption Demity (mg/m2)
pH=ll.O
Initial PAX
pH4.0
pHe7.0
pH=9 .O
pH= 12.0
Test
No.
Concentration
(mm
1
10.0
20.0
50.0
2,060
1.996
1.885
1.976
1.533
4.007
4.100
3.991
3.568
2.326
1:143
5.000
4.620
5.125
3.438
Equilibrium Adsorption Of PAX On Synthetic Enargite
Initiai Conditions
Concentration
Aliquot
Chart Value
Concentration
mg in Solution
(mR/1)
(mdl)
(mm
Solution pH = 6.0
10.00
10
0.530
10.00
Straight
20.00
20.00
20
1.060
50
5/50
50.00
50.00
2.650
Solution pH = 12.0
10
straight 1
10.00
10.00
0.530
20
20.00
20.00
1.060
50
5/50
50.00
50.00
2.650
Solution pH = 9.0
Mah
.. 1 20.00-200+325
20
1
1
20.00
1
1.060
Final Conditions
Aliquot
Chart
Equilibrium
mg in Solution
Adsorption
mg
Value
Adsorbeci
Conc. (rng/l)
Densi-
2
3
1
Test
NO.
1
2
3
ba
1
2
3
b
.
(mR/I)
mglg
1
Straight
Straight
Straight
Solution pH = 6.0
0.0 16
0.3 1
0.71
0.037
0.3 1
0.7 1
2.79
11-10
1.028
2.036
0.5 15
1.023
mgm2.060
4.106
Solution pH = 12.0
2.79
1
0.148
0.383
0.765
1.533
Solution pH = 9.0
-2OO+3 25 Mesh
11.10
1
0.588
0.172
( 0.944
3.852
Table 4.1.1.6
Test Conditions
Air Fiow Rate=300 mi/mk, Aeration Time=2O min.
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min
Bottle voiume = 53.0 mi, Agitated at 30 r.p.m and Centrifiiged for 30 seconds
initial Conditions
Test
Xanthate
Aiiquot
Chart Value Concentration
mg in Solution
No. Concentration
mg/l)
mgm
mm
20
Aliquot
Chart Value
(mgfl)
20.00
20.00
Final Conditions
EquiIibrium mg in Solution
mg
Conc. (mR/1)
Adsorbed
1.060
Adsorpuon
Density
Test
No.
Xanthate
Concentration
notation Recovery
O'?
(md)
With
Amy1 Xanthate
1
0.0
2
3
1.O
5.O
10.0
3 -20
33.05
53.65
68.60
With
Ethyl Xanthate
3.20
24.10
48.25
62.10
Table 4.1.2. la
The Effect Of Sodium Cyanide Concentration And Contact Time On The Floatability Of
Synthetic Euadte
Xanthate Concentration = 20.0 mg& pH9.0
% Recovery
Test No. Time (min.)
NaCN Concentration 1 NaCN Concemarion ( NaCN Concentration
Table 4.1.2. lb
The Effect Of Sodium Cyanide And Xanthate Concentration On The
Fioatability Of Svnthetic Enargite
Constant NaCN & Increased Xanthate Concentration
Test No.
2
3
4
Time (min.)
0.0
0.5
1 .O
2.0
5.O
20.0
% Recovei
PAX Concentration
PAX Concentration
74.95
18.60
13.70
15.38
18.55
23.60
79.30
47.00
33.75
27.50
24.38
34.00
h
TabIe 4.1.2.1 c
The Effect Of Sodium Cyanide And Particle Size Ou T h e Floatability Of
Syntbetic Enargite
Xanthate Concentration 20.0 mg/l
NaCN Concentration = 15.0 rnR/I. p H = 9.0
% Recovery
Test No. 1 Time (min.) 1
-20W325Mesh
-325 Mesh
74.95
1
0.0
7625
2
3
4
5
6
0.5
1 .O
2 .O
5 .O
18.60
13.70
t 5-38
18.55
30.0
23.60
23.75
18-13
18.56
22.40
24.50 -
Table 4.1.22
The Effect Of Sodium Sulphide Concentration And Contact Time On
The Floatability Of Synthetic Enargite
Xanthate Concentration = 30.0 mgIl, pW9.0
Test No. 1 Tirne (min.) 1
% Recovery
1
1
1
NazS Concentration
Table 4.1.2.3a
The Effect Of Flotation pH & pH Regulators On The Floatability Of
Svnthetic Enargite
PAX Concentration = 20.0 mgil
Test No.
% Recovery
pH
NaOH
Ca0
1
78.40
78.40
6.0
74.95
2
9.0
712 5
3
4
11.0
12.0
71.15
24.83
69.85
20.2 1
Table 4.1.2.3b
The Effect Of pH & PAX Concentration On The Floatabiiity Of Synthetic
Enargite
est 1
PAX
I
94 Recovery
No.
Concentration
(mR/1)
Table 4.1.2.4a
The Effect Of pH & K M ~ O Concentration
I
On The Floatabiity Of Synthetic Enargite
PAX Conantration = 20.0 mp/t
Test
KMnOd
% Recovery
No. Concentration
(me/l)
Table 4.1.2.5
74.95
0.0
TabIe 41.2.6
. The EffectOf Aeration Conditioning On The FloatabiIity Of Synthetic Enargite
% Rotation Recovery
74.95
Table 4.1. Ja
No.
PAX Conc.
PAX Conc.
10.0 rnfl
pH = 6.0
0.0 mgi
PAX Conc.
20.0 mgil
PAX Conc.
50.0 mg11
s
pH = 9.0
Ave.
8.3
80.4
Ave.
7.5
Ave.
3.8
65.8
1
pH = 11.0
62.6
1
76.9
80.2
74.1
76.8
Table 4 1 . 4 ~
The Effect Of NaCN Concentration On Contact Angle Of Synthetic Enargite
PAX Concentration = 20.0 mR/1
TestNo. 1
Contact Angie (Degree)
NaCN Concentration = 0.0 mR/I
pH = 6.0
pH = 9.0
pH = 11.0
Ave.
77.4
76.9
74.1
NaCN Concentration = 5.0 mg/l
Ave.
57.7
Ave.
3 1.7
Ave.
18.2
1
56.0
N a m Concentration = 10.0 rn@
I
1
27.8
NaCN Concentration = 15.0
1
12.8
ma
55.3
23.5
8.2
Table 4.1.7
Zero Point Of Charge Of S-vntheticEnargite
The Adsorption Of Potentiai Determinhg Ions Technique
Sample Welght = 4 g, Spedic S&ce Area = 0.4991 g/m2
1.000 mi of 1.181N NaOK 400 ml of O.IN KCL 1.00N HCI
Test No.
Acid (ml)
Blank
With Enargite
2.76
1
3.45
2.88
2
2.90
3.O0
3
3.50
4
3.O6
2.20
5
3.10
2.45
6
3.17
1.80
7
3-3
2.00
8
3 -41
1.50
9
3.42
1.85
IO
3.58
1.JO
11
3.71
1.30
3.76
12
1.55
Table 5.1. la
Adsorption Of Potassium Amvl Xanthate On Natural Enargite As A Function Of Time
Test Conditions
I
Test
No.
I
2
3
J
5
6
&
.
bb
..
.b
b
.
I
2
3
4
5
Straight
10
CL
20
50
100
200
bb
Aiiquot
20/100
10/100
Y100
Chart
Vaiue
Straight
b
0.32
0.41
5-00
5.O0
10.00
10.00
20.00
20.00
50.00
10.00
100.00
f 0.00
200.00
10.00
Final Conditions
Equilibrium
mg in
Concentration
Solution
0.32
0.41
0.017
0.022
0.265
0.530
1 .O60
2.650
5.300
10.600
mg
Adsorbeci
0.248
0.508
Adsorption Denst p-
mg&
mwm-
0.496
1.017
0.687
1.408
Table 5.1.1.1
The Effect OfSodium Cyanide Concemtratioa And Contact Time On The Pre-Adsorbed Xanthate
On Naturai E n a M e
initial Xanthate Concentration = 20.0 mg/i = 1.060 mg & pH = 9.0 Modifieci With NaOH
Test
NaCN
Contact
Fiilal Xanthate
Adsorption
Adsorption Density
mg
No.
Conc.
Te
Concentration
Xanthae
(mg)
(mdl)
in Soiution
(wu
(mm
Table 5 . l . l . l b
The Effect Of NaCN On Adsorption Density Of PAX On Naturat Enargite
Test Conditions
NaCN Concentration = t 5.0 mg/I. Conditioning Tirne= 1O min.
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bode volume = 53.0 mi. Agitated at 30 r.p.m. and Centrifueed for 30 seconds
Initiai Conditions
Test
Xanthate
Aliquot
mg in Solution
Chart Value Concentration
No. Concentration
(mg(l)
(mgfi)
(mfl)
1
10.00
Straight
10
10.00
0.530
7
20
AIiquot
Chart Value
20.00
20.00
Final Conditions
Equilibrium
mg in
Conc. (mg/i)
Solution
1.O60
mg
Adsorbed
Adsorption
Density
',
Table 5. l. 1.2
Effect Of Sodium Sulphide Concentration And Contact Time On The Pre-Adsorbed Xanthate
On Naturai Enamite
Initiai Xantbate Concentration = 20.0 rngA = 1.060 mg & pH = 9.0 Modifieci With NaOH
F i Xanthate
Adsorption
Contact
Adsorption Density
Na$
Test
mg
Concentration
Xanthate
Tirne
Conc.
No.
(mg)
in Solution
(mm
(m*.)
mm
rnglmmg&
1 The
1
2
3
4
10_0
10.0
10.0
10.0
0.0
0.5
1.0
2.0
5.0
0.52
1.58
3.O5
3.61
4.30
0.027
0.084
0.162
O. 19 1
0.228
2,066
1.034
0.976
0.898
0.869
0.833
2.859
2.703
1.953
1.797
2.487
1.738
1.665
2.406
2.305
Table 5.1.1.2b
Aiiquot
Chan Value
(mm
Final Conditions
Eqtdibrium
mg in
Conc. (mg/l)
Solution
mg
Adsorbed
Adsorption
Density
Table 5.1-1.3
The Effect Of KMnO, Concentration And Contact Time On The PreAdsored Xanthate
-
- - -
Test
No.
Initial &hate
KMnOJ
Conc.
Aliquot
1 Chartwt /
Chart Value
(mm
1
2
Straight
L
3.58
7.01
(ma)
Final Conditions
Equilibrium
mg in
Solution
Conc. (mgII)
3.58
7.0 1
O.190
0.371
mg in Solution
Concentration
mg
Adsorbed
0.340
0.689
Adsorpuon
Densimgimmg&
0.681
0.943
1.378
1.907
Table 5.1.1.4
The Effect Of p H On Adsorption Deasity Of PAX On Naturai Enargite
Test Conditions
Sample weight = 0.5000 g, pH Adjusteci with NaOH Adsorption urne = 60 min.
Bortle volume = 53.0 ml. Agitateci at 30 r.p.m. and Centrifugeci for 30 seconds
Initial Conditions
Xanthate
Aliquot
Chart Value Concentration
mg in Soiution
Concenmuon
(mg/i,
Test
No.
mm
Straight
20
Straight
20
Svaight
20
Chart Value
Aliquot
Solution pH = 6.0
20.00
1 20.00
Solution pH = 11 .O
20.00
1 20.00
Solution pH = 12.0
20.00
1 20.00
Final Conditions
mg in
Equdibnwn
Conc. (mg;/l)
Solution
(ma)
Straight
0.41
Straight
8.97
Straight
14.70
Solution pH = 6.0
0.4i
1
0.022
Solution pH = L 1.0
8.97
14.70
0.475
Solution pH = 12.0
0.779
1.060
1.060
1 .O60
Adsorption
Densiw
mg
Adsorbed
1.038
0.585
) 1.170 ( 1.619
0.281
2.077
2.875
0.562 ( 0.778
Table 5.1.1.5
The Effect Of Aeration On Adsorption Densitv Of PAX On Naturd Enargite
Test Conditions
Air Flow Rate=300 &min.. Aeration Time=20 min.
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bottle volume = 53.0 ml. Agitated at 30 r.p.m. and Cenuifiiged for 30 seconds
Initiai Conditions
Chart Value Concentration
mg in Solution
Test
Aiiquot
Xanthate
Concentration
ru'o.
(mg/I)
20.00
1.060
1
20
20.00
Final Conditions
Chart Value Equilibrium mg in Solution
mg
Adsorption
Aiiquot
Adsorbed
Density
Conc.
(rng/i)
(m@)
(ma)
(ma)
Straight
6.87
6.87
0.364
0.696
1.392
1.926
Table 5.1.2
Boatabilitv Of Natural Enargite
I
1
Test No. 1
p H = 9.0
Xanttiate
1 Concentration (rnR/I)
1
(
Notation h v e r y
?40
1
1
Table 5.1.2.1
Test No.
Table 5.1.2.2
The Effect Of Sodium Sulphide Concentration And Contact Time On The
FloaGbiiity Of Natural Enargite
Xanthate Concentration = 20.0 mg/l. pH = 9.0
Test No. Tirne (min)
% Recovery
Na2S Concenuation
1 NazS Concentration
Table 5.1.2.3
The Efllect Of pH On The FIoatability Of Naturai Enargite
Table 5.1.2.4a
The Effect Of pK & KMnOi Concentration 0t?he Fioatability Of Natural Enargite
PAX Concentration = 20.0 mfl
Test
% Recovery
No. Concentration
Table 5.1.2.5
The EffectOf Aeration Conditioning On The Floatability Of Natural E n a a t e
PAX Concentration = 20.0 m@i. pH = 9.0
TestNo. 1
Aeration Time (min.)
1
% Flotation Recovec
.1
Table
- -- - - 6
-.
-1
- - -la
Adsorption Of Potassium Amyi Xautbate On Chaicopyrite As A Function Of Time
Test Conditions
ple weight = 0.5000 g, Solution pH = 9.0 (Adjusteci with NaOH)
6
7
I
120.0
180.0
..
6.26
5.02
0.331
0.265
2.3 19
2.385
4.638
7.1JO
4.770
7.343
Table 6.1. lb
I4
Test Conditions
Sample weight = 0.5000g, SoIution pH = 9.0 (Adjusted with NaOH). Adsorption time=120min.
Bottie volume = 53.0 ml. Agitateci at 30 r.p.m and Centfigeci for 30 seconds
Initial Conditions
mg in Solution
Test Xanthate Aliquot
Chart Value
Concentration
No.
Conc.
(WYl)
mm
mm
1O
20
50
100
200
300
400
500
3
4
5
6
7
8
9
Aliquot
Straight
U
(L
20lIOO
101100
9100
31100
2/100
11100
Cbart
Value
mgm
5-10
5.10
10.70
10.70
20.00
20.00
10.00
50.00
100.00
10.30
200.00
10.00
300.00
10.00
j00.00
10.00
500.00
10.00
Final Conditions
Equifibrium
mg in
Concentration
Solution
mm
0.270
0.567
1.060
2.650
5 .+59
10.600
15.900
21.200
26.500
*g
Adsorbeci
Adsorption Density
Table 6.1.1.1
1 The Ef'fect Of Sodium Cyanide Concentration And Contact Time On The PreAdaorbed Xanthafe [
1
On Chaicopyrite
1
Initial Xanthate Concentration = 20.0 mp;ll= 1.060 mg & pH = 9.0 Modifie. With NaOH
Test
NaCN
Conc.
(mm
No.
Contact
The
(min.1
F i Xanthate
Concentration
(me/i)
mg
Xantbak
in Solution
Adsorption
Adsorption Density
(mg)
Table 6.1.1. lb
Straight
10
20
Aliquot
10.00
20.00
Chart Value
(mm
Straight
3.21
64
6.26
10.00
20.00
Equilibrium
Conc. (mN)
3.2 1
6.26
0.530
1.060
mg in
Solution
O. 170
0.332
mg
Adsorbed
0.360
0.728
Adsorption
Density
mgig
0.720
1.456
mg/m2
1.108
-
2.232
1
1
Table 6.1.1-2
The Effect Of Sodium Sulphide Concentration And Contact Time On The Pre-Adsorbed Xanthate
initiai Xanthate Concentration = 20.0 mg/l= 1.060 mg & pH = 9.0 Modifieci With NaOH
NazS 1 Confact 1 Finai Xanthate 1
mg
1 Adsorption ( Adsorption Density
No.
Conc. 1 fime
1 Conannation 1 xanthate 1 (mg) 1
Test
1
1
Test Conditions
Na2S Concentration = 10.0 mg& Conditioning T i e = l O min.
Sampte weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH), Adsorption time = 60 min.
Bottle volume = 53.0 ml. Agitated at 30 r.p.m. and Cenmgeci for 30 seconds
Initial Conditions
Test
Xanthate
Aliquot
Chart Value Concentration
mg in Solution
No. Concentration
mgn)
(ma)
(mm
10
Straight
10.00
10.00
0.530
Final Conditions
Aliquot
1
Suaight
Chart Value
Equilibrium
(mg/l)
Conc. (ma)
mg in
Solution
Adsorbeci
6.92
13.61
6.92
13.61
0.367
0.721
O. 163
0.339
mg
Adsorption
Density
mdmmgig
0.503
0.327
0.678
1.044
Table 6.1.1.3
The Effect Of KMnO, Concentration And Contact Time On The Pre-Adsorbed Xanthate
On Chaicopvrite
Initial Xanthate Concentration = 20.0 mg/i = 1 .O60 mg:& pH = 9.0 Modified With NaOH
Contact
W O o
Finai Xanthate
Adsorption
Adsorption Density
mg
Conc.
Tirne
Concentration Xanthate in
(mg)
Solution
(me;/I)
(dl
(mgfi)
Test
No.
1
Table 6.1.1.3b
The Effect Of KMnO. On Adsorption Density Of PAX On Chalcopyrite
Test Conditions
'
(mgn)
10
20
Straight
Aiiquot
Chart Value
(mgfi)
10.00
10.00
20.00
20.00
Final Conditions
Equilibrium
mg in
Conc. (md)
Solution
0.530
1.O60
mg
- Adsorbeci
Adsorption
Density
Table 6.1.1.4
Test
No.
1
2
1
2
1
2
1
Tesi Conditions
Sample weight = 0.5000g, pH Adjusted with NaOK Adsorption time = 120 min.
Bode volume = 53.0 m i Agjtated at 30 r.p.m. and Centrifugecl for 30 seconds
initial Conditions
Xanthate
Aiiquot
Chart Value Concentration
mg in Solution
Concentration
(m@)
(mgAl
Solution pH = 6.0
20
Straight
20.00
20.00
1 .O60
50
201100
50.00
10.00
2.650
Solution pH = 7.0
20
20.00
Straight
20.00
1.060
50
201100
50.00
10.00
2-650
Solution pH = 1 1.0
20
Straight
20.00
20.00
1.060
50
201100 10.00
50.00
2.650
Solution pH = 12.0
20
Straight
20.00
20.00
1 .O60
50
201100
I0.00
50.00
2.650
Final Conditions
Aliquot
Chart Value
Equilibrium
mg in
Adsorption
mg
Conc. (mM)
Solution
AdsoM
Densiw
(mm
mm
mgig
1
2
Straight
Straight
7
B
Straight
2
1
1.12
3.5 1
Straight
4/25
1
1
1.3 1
4.99
6.19
16.72
1 1.50
3.83
Solution pH = 6.0
0.059
1.12
O.186
3.51
Solution pH = 7.0
1.31
0.069
0.264
4.99
Solution pH = 1 1.0
6.19
0.328
16.71
0.885
Solution pH = 12.0
11-50
0.610
30.20
1.600
1 mdm2
1.001
2-43
2.002
4.930
7.589
0.99 1
2.386
1.982
4.773
3.051
7.348
O. 732
1.464
1.765
3.530
2.253
5.434
0.451
1.050
0.901
2.100
1.387
3.233
3.082
Table 6 - 1 - 1 3
The Effect Of Aeration On Adsorption Density Of PAX On Chalcopyrite
Test Conditions
Air FIow Raw300 dmin.. Aeration Tie=20 min.
Sample weigbt = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH), Adsorption t h e = 60 min.
Bottie volume = 53 -0 mi. Agitami at 30 r.p.m and Centnfuged for 30 smnds
initiai Conditions
Xanthate
mg in Solution
Test
Chart Vaiue Conccnaation
Aiiquot
No. Concentration
<mm
mm
(mm
n
20
20.00
Chart Vaiue
Aliquot
Straight
6.88
Test No.
1
1
1
20.00
1.O60
l
mg
Conc. (mgB)
(mm)
1 1
Final Conditions
Equiiiirium mg in Solution
6.88
Adsorbeci
0.364
0.695
Adsorption
Dcnsity
mg/m2
mglg
1.391
Table 6.1.2
Floatability Of Chalcopyrite
pH = 9.0
Fiotation Recovery
Xanthate
Concentration (m@)
'%O
0.0
6.95
TabIe 6.1.2.1
The E f f Of
~ Sodium Cyanide Concentration And Contact Time On
The Fioatabiiity Ot Chaicopyrite
Xanthate Concentration = 20.0 mg/L pH = 9.0
Test No. Tirne (min.)
% Recovery
NaCN Concentration 1 NaCN Concentration
2.141
Table 6.1.2.2
Table 6.1.2.3
The E f k t OC pH On The Floatability Of Chahpyrite
PAX
%Recovely
Concentration
Test
No.
Table 6.1.2.4a
KMn0.4
Concentration
Chaicopyrite
PAX Concentration = 20.0 mg/l
% Recovery
(mg)
1
2
3
pH = 6.0
82.95
0.0
10.0
25 .O
50.0
100.0
pH = 9.0
pH = 12.0
80.65
77.40
69.00
25.50
39.42
5 1.82
38.85
27.30
Table 6.1.2.5
ma.pH = 9.0
% Flotation Recovev
80.65
&
Table 7.3.6
Ttie Effect Of Pulp Potentiah On The Fioatability Of Synthetic Enargite,
NatUrPi Enniljte And Cbaicopyrite
PAX Concentration = 20.0 rnfl p H = 9.0
Naturai Enargite
1
Chalcopyrite
1
1
1
1
mm
mgig
b
2
3
4
1
2
3
J
5
6
0.0
100.0
150.0
200.0
12.84
Synthetic Enarate
0.064
0.171
0.308
0.680
0.0
100.0
150.0
200.0
250.0
300.0
0.52 .
1.84
3.60
8.99
15.22
15.74
Natural Eaargte
0.027
1.034
0.097
0.963
0.191
0.869
0.477
0.583
0.807
0.253
0.834
0.226
1.22
3 .23
5.81
0.996
0.889
0.752
0.380
mdm-
1.992
1.778
1.504
0.759
3.99 1
3.562
3.014
1-521
2.066
1.925
1.738
1.167
0.507
0.452
2.665
2.106
1.615
0.702
0.625
2.859
Table 9.3,lb
The Effect Of pH And MAA On The Adsorption Density Of PAX On Synthetic Enargite,
Test
1 No. 1
mg&
0.254
0.516
1.945
0.510
0.714
2.994
0.244
0.507
1.787
0.488
0.702
2.75 1
O.192
0.381
1.413
0.384
0.527
2.175
pH = 7.0
1
2
3
S-vntheticEnargite
Natural Enargite
Chalcopyrite
17.61
15.13
1.66
Synthetic Emgite
Natural Enargite
Chalcopyrite
17.70
15.22
3.15
2
3
0.933
0.802
0.088
pH =9.0
0.938
0.807
O.166
pH = 11.0
0.964
0.870
0.354
S-ynthetic Enargte
18-19
Naturai Enargite
16.41
Chaicopyrite
6.67
pH = 9.0.Aeration 10 Min.. nien
S-vnthetic Enargxte
17.78
Naturai EnarMte
15.90
Chalcopyite
3.14
2
3
1
2
3
O.127
0.258
0.973
O.122
0.253
0.894
0.096
O.190
0.707
IO Min. Conditioning With
O. 118
0.942
0.217
0.843
0.894
0.166
MAA
0.235
0.435
1 .788
0.471
0.602
2.753
Table 9.3.lc
Test
No.
mg/g
I
2
3
4
2
3
4
0.0
5.0
10.0
20.0
1.12
11.13
17.70
17.74
0.0
5.0
10.0
20.0
0.52
9.82
15.22
15.32
Synthetic Enargite
0.064
0.996
0.590
0.470
0.938
0.122
0.940
O.120
Natural Enargite
0.027
1.033
0.539
0.521
0.807
0.253
0.248
0.812
mdm-
1.992
0.941
0.244
0.240
3.99 1
1.885
0.488
0.480
2.066
1.079
0.507
0.496
2.859
1.393
0.702
0.686
pH = 9.0
(mg/i)
1 Solution 1
ci sorbe ci
1
2
3
ChaiCopyrite
3.15
0.167
0,893
PAX Concentration = 30.0 m@ = 1.590 mg
Synthetic Enargite
27.19
1.441
O. 149
Natural E n d t e
24.32
1.289
0.30 1
Chaicouvrite
3.95
0.209
1.381
1
2
3
1
0.244
0.507
1.787
0.488
0.702
2.75 1
0.297
0.602
2.76 1
0.596
0.833
4.25 1
Table 9.3.2a
mg/i
N a d
Enargite
Chaicopyrite
Enargite
74.95
65.63
58.71
71.25
63.12
56.73
80.65
79.8 1
79.62
Synthetic
1
r
2
3
0.0
100.0
150.0
Table 9.3.2b
The Effect OfpH And MAA On The Floatabity Of Synt&etic Enmgite,
Naturai Enargite And Chalcopvnte
MAA Concentration = 250.0 m f l Conditioning Time = 10 Min-
Test No. [
O/oR
2
3,
1
2
Synthetic Enargite
Na-
pH = 7.0
9.79
14.90
82.60
pH = 9.0
pH= 11.0
9.24
14.53
80.40
6.89
9.75
46.60
Enargite
Cbaicopyrte
Aeration = 10 min,. Then Conditioning With M U
Synthetic Enargite
6.90
Naurai Enargite
12.2 1
Chalcopyrite
79.20
PAX Concentration = 30.0
Syuthetic Enargite
11.28
Naturai Enargite
16.07
ma
Table 9.3.3a
The Effeft Of Surface Tension Regdated By Methmol On The Foatability Of
Svnthetic Enargite, Natural Enargjte And Chalcopyrite
PAX Concentration = 20.0
pH = 9.0
%
Test
Surface
%R
No. Methanoi Tension
(dynes/cm)
Synthetic
1 Natural 1 Chacomte
Enargite
Enargite
ma,
2
3
4
100
50
JO
25
15
22.6
34.8
39.9
46.2
53.1
14.87
35.22
62.4 1
68.59
11.21
26.07
47.32
58.91
6.98
21.27
68.05
77.92
Table 9.3.3b
The E f f t Of Surface Temion Regulated By Metfimol On The Floatabifity Of
S-vathetic EnNatural Enargjte And Chalcop~nte
MAA Concentration = 250.0 rng/l, Conditioning T i e = 10 Min.
Test
No.
Methano1
,
,
Synthetic
Nafurai
Champyrite