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FLOTATION CHEMISTRY OF E N U G I T E AND CEALCOPYRITE

USING POTASSIUM AMYL XANTBATE AND DEPRESSANTS

Jalai Tajadod

A thesis subrnitted to the Department of Mining Engineering

in confonnity with the requirement for the degree of


Doctor of Philosophy

Queen's University
Kingston, Ontario, Canada
June, 1997

Copyright O Jalaf Tajadod, 1997

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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.

His encouragement and patient discussions are deeply appreciated.


Sincere thanks are extended to Mr. Alan Pindred for his advice and assistance in the
Mineral Processing laboratory.
Speciai thanks are due to Dr. James F. Archibaid, Dr. Panagiotis D. Katsabanis. iMrs.
Bev McCaiium and Mrs. Wanda Badger for their CO-operationand support during this

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

LIST OF FIGURES ..................................................................................................................................


XI
LIST OF TABLES ................................... ............................................................................................. x'vii
LIST OF ABBREVIATIONS .................................................................................................................. u x

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

2.3. 1 Chernical or Solubility Theory.....................................................................

2.2.2 The Neutrd Molenile Theory ................

10

.
.
................................................ 10

7.2.3 Ion Exchange Theory .....................


.
............................................................. 1 1
2.74 Electrochemical Mode1 Theory ........................................................................ 14
2 . 3 Rc )LE O F OXYGENIN XANTHATE ADSORPTION........................................................

15

2.4 E~.ECTRICU
ASPECTS OF XAMHATE CEMISORPTION ON SULPHIDE
MJNERALS ...... 16
2.4. 1 Electncal Double Layer ...................................................................................

16

2.4.1.1 Application to Flotation Systems ........................ .


.
.
................................. 70

3. 4.2 SemiconductorfSolution Interface .................................................................

3.5 ELEC-I-ROCHEMISTRY
OF SULPHIDE
M ~ M SFLOTA~ON
..............................

22
...... 27

.
,

3.5.1 Mechanism of Collecter-Induced Flotation ...................................................... 30

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

3 2 . 3 Contact Angle Measurements .......................................................................... 59


3.2.4 InFrared Absorption Study ...............................................................................

60

3.2.5 Mineral Solubility ............................................................................................

60

3 .2.6 Zero Point-of-Charge Measurernents ...............................................................

61

3.2.7 Rest Potentid Study ........................................................................................

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

4.1.1.1 Effect of Sodium Cyanide on Adsorption ...................................................... 68


4.1.1.2 Effect of Sodium Sulphide on Adsorption ..................................................... 69
4.1 . 1 .3 Effect of KMn04 on Adsorption ................................................................... 71

4.1 . 1.4 Effect of Copper Sulphate on Adsorption ..................................................... 72


4.1.1.5 Effect of pH on Adsorption .......................................................................

73

4.1.1.6 Effect of Aeration on Adsorption .................................................................. 75

4.1.3.1 Effect of Sodium Cyanide on Flotation .......................................................... 77


4.1.3.2 Effect of Sodium Suiphide on Flotation......................................................... 80
4.1.2.3 Effects of pH and pH Regdators on notation ............................................... 82
............................................. 83
4.1.2.4 Effect of KMnO4 on Flotation ...........
.
.
.

4.1.2.5 Effect of Copper Suiphate on Flotation ......................................................... 85


4.1 .2.6 Effect of Aeration on notation .................................................................... 86
4 1.2.7 Effect of Pulp Potentials on Rotation .........................................................

88

1 . 1 .3 Adsorption-Flotation Relationship .....................


.
...................................... 89
4.1.4 Contact Angle of Synthetic Enargite ................................................................ 90

41

Infrared Absorption Spectra of Synthetic Enargite ...........................................93

4 . 1.6 Solubility of Synthetic Enargite ........................................................................

93

1 1 7 Zero Point-of-Charge of Synthetic Enargite .....................................................

94

4 1.8 Rest Potential o f Synthetic Enargite ................................................................. 95

4.2 DISCUSSION
........................................................................................................... 97

4.2.1 Adsorption ......................................................................................................

97

1.2.2 Flotation ........................................................................................................

101

4.2.3 Effect of Sodium Cyanide ..............................................................................

102

1.2.3 Effect of Sodium Sulphide .............................................................................

105

4.2.5 Effect of KMn04 ................................................................ ........................... 106

4.2.6 Effect of Copper Sulphate .............................................................................

107

4 2 . 7 Effect of pH ........................
...

108

....................................................................

-12.8 Effect of Aeration .........................................................................................

IO9

4.3.9 Effect of PuIp Potentials ................................................................................

110

4.2.10 Contact Angle of Synthetic Enargite ............................................................ 113


4.2.1 1 Infrared Absorption Study ...........................................................................

114

4.2.12 Solubility of Synthetic Enargite .................................................................... 115


4.2.13 Zero Point-of-Charge of Synthetic Enargite ................................................ 115
4.2.14 Rest Potential Studies ..................................................................................

116

4 .3 CONCLUSIONS...................................................................................................... 117

CWTER5
FLOTAIION CHEMISTRY
OF N

AE N A ~
RG
..........................................................
~
120

5 1 RESULTS ..............................................................................................................
.

120

5 1. 1 Adsorption .................................................................................................... 120


.

5.1.1.1

Effect of Sodium Cyanide on Adsorption .................................................... 122

5.1.1.2 Effect of Sodium Sulpbide on Adsorption ................................................... 123


5.1 - 1-3 Effect of - 0 4

on Adsorption ................................................................. 124

5.1. 1 4 Effect of pH on Adsorption ........................................................................ 126


5 . 15 Effect of Aeration on Adsorption ................................................................ 126
5.1.2 Flotation ............

............................................................................
.
.
.
.

127

5.12 1 Effect of Sodium Cyanide on Flotation ....................................................... 127


5 . 1 2 . 2 Effect of Sodium Sulphide on notation ......................................................

129

5 . 1 2 3 Effect of pH on Flotation ................ .


.
.
.................................................. 130

5.1.2.4 Effect of KMn04 on notation .....................................................................

131

5.1 2 . 5 Effect of Aeration on Flotation ...................................................................

133

5.1.2.6 Effect o f Pulp Potentials on Flotation.......................................................... 133


51.3 Adsorption-Flotation Relationship ................................................................. 135

..............................................................................
6.1 RESULTS ...................... .
.
.

6.1.1 Adsorption ....................................................................................................

139
139

6.1.1.1 Effect of Sodium Cyanide on Adsorption .................................................... 141

6.1.1.2 Effect of Sodium Sulphide on Adsorption ................................................... 142


6.1.1.3 Effect of KMnO4 on Adsorption ................................................................. 144
6.1. 1.4 Effect of pH on Adsorption ........................................................................

145

6.1. 1 .5 Effect of Aeration on Adsorption ................................................................

146

6.1.2 Flotation ........................................................................................................

147

6.1.2.1 Effect of Sodium Cyanide on Rotation ....................................................... 148

6.1.2.2 Effect of Sodium Sulphide on Rotation ....................................................... 149


6.12 . 3 Effect of pH on Rotation ............................................................................

150

6.1 .2.4 Effect of KMn04on Flotation ..................................................................... 151

6.12 . 5 Effect of Aeration on notation .................................................................. 153


6.1.2.6 Effect of Pulp Potentials on Flotation .....................................................

154

6 - 1 3 Adsorption-Flotation Relationship ................................................................

155

.........................................................................................................
6.2 Drscussro~

157

Adsorption ....................................................................................................

157

Flotation ......................................

158

Effect of NaCN .............................................................................................

159

Effect of Sodium Sulphide .............................................................................

160

J
Effect of K M ~ O........................................................................................

161

Effect of pH ........................ .
.
.
............................................................... 162
Effect of Aeration ...................................

.....................................................

163

Effect o f Pulp Potentials ................................................................................

163

CHAPTER 7

COMP.~RISON
OF m FLOTATIONCHEMISTRY
OF SYNTHETIC
ENARGITE
NA^ ENARGITE
AND CHALCOPYRITE
....................................................................

INTRODUCTION

166

....................................................................................................

166

7.2 ADsWtN ........................................................................................................

167

7.1

7.2.1 Effect of Sodium Cyanide on Adsorption ....................................................... 170


7.2.2 Effect of Sodium Sulphide on Adsorption ...................................................... 173
7.2.3 Effect of Kh4n04 on Adsorption ....................................................................

175

7.2.4 Effect of pH on Adsorption ........................................................................... 176


...
7.2.5 Effect of Aeration on Adsorption ...............

.............................................

177

7.3 FLOTATION ..........................................................................................................

178

7.3.1 Effect of Sodium Cyanide on Flotation ..........................................................

179

7.32

Effect of Sodium Sulphide on Flotation ......................................................... 181

7 2 . J Effea of pH on Notation ...............................................................................


7

182

7.3.4 Effect of KMn04 on notation........................................................................ 184

7.3.5 Effect of Aeration on Rotation ...................................................................... 185


7.3.6 Effect of Pulp Potentiais on Rotation .............
.
.
.
................................... 187
7 J LMORATORY SCALEFLOTA~ON
.........................................................................

188

7.5 CONCLUSIONS
...................................................................................................... 189

CEUPTER 8

REDUCTON

OFTHE ARSENICCOMENTINCOPPERCONCENTRATES
......................-....... 191

8.1 [NIRoDUCTION ....................................................................................................

191

......................................................................................
8.2 SEPARATIONFLOTAT~ON

193

8.2.1 Expenmental Techniques ............................................................................... 193


8.2.2 Results .......................................................................................................... 194

8.2.3 Discussion .....................................................................................................

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 ............................................................................................................

9.3.1 Adsorption ....................................................................................................

201

201

9.3.2 Flotation ........................................................................................................ 205

9 . 3 3 Surface Tension Studies................................................................................. 208


9.3.4

Selective Depression of Enargite................................................................... 211

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

REFERENCES .......................................................................................................... 223


APPENDICES
Appendix A l

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

METHODOF CHEMICALANALYSE ................................................................................ 23 9


Appendix A8

METHODOF SULPHUR ANALYSIS.................................................................................. 24 1


Appendix A9
TA~ULATIONOF ExPEIUMENTAL

RESULTS.................................................................... 242

LIST OF FIGURES
Page
Figure 2.4.1 : The structure and potential gradient of an electrical double layer. ............. 19

Figure 2.4.2a: ...-................


.,.,.

...~-.-...-.--.-..-................................................................
24

(a) Schematic representation of perfect diamond lattice


(b) Conduction eIectron in diarnond
(c) Holes in diamond
(ci) Motion of a hole through the diamond lattice

Figure 2.4.2b: Semiconductor band structure. ............................................................... 26

Figure 2.7: Schematic representation of equilibnum contact between


an air bubble and a solid immersed in a liquid. ............................................................... 39

Figure 2.10 1a: Enargite composition in the Cu-As-S system in atom percentage. ........ .46

Figure 2. 10. 1b : Crystal structure of enargite. .......................... .


.
.
.
.......................... 46
Figure 2.10.2a: Chalcopyrite composition in the Cu-Fe-S system. ................................. 48
Figure 2.10.2b: Crystal structure of chalcopyrite ................................
. ..
..
.
. .

49

Figure 4 - 1 1a: The adsorption of potassium amyl xanthate on synthetic enargite as a


function of time at pH 9. ................................................................................................ 63
Figure 4.1.1 b: Adsorption and desorption isotherms for PAX on synthetic enargite
at pH 9. ........................................................................................................................ 64

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

...

mg/l initial xanthate concentration............................................................................. 7 1


F i e 4 11.4: The effect of copper sulphate concentration on the adsorption
density of PAX on synthetic enargite at pH 9. ................................................................

73

Figure 4.1.1.5a: Equilibnum adsorption of PAX on ynthetic enargite at


different pH values. .......................................................................................................

74

Figure 4.1 .1.5b: The effect of pH on the adsorption density of PAX


on synthetic enargite. ..................................................................................................... 75
Figure 4.1 .2 : Floatability of synthetic enargite. .............................................................. 76
Figure 4.1.2.1a: The effect of sodium cyanide concentration and contact time on the
floatability of synthetic enargite at pH 9 and 20 mgA PAX concentration. ...................... 77
Figure 4.1.2.1b: The effect of sodium cyanide contact time and xanthate concentration
on the floatability of synthetic enargite at pH 9 and 15 mg/l sodium cyanide................... 79
Figure 4.1.2.1c: The effea of sodium cyanide contact time and particle size on the
floatability of synthetic enargite at pH 9, PAX concentration of 20 mg/i and
1 5 mg/l cyanide concentration......................................................................................

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

Figure 4.1.2.3 b: The effect of flotation pH and P A X concentration on the


...
floatability of synthetic enargite. ..........................

83

...................................................

Figure 4.1 .2.4a: Floatability of synthetic enargite as a function of KMnOJ


concentration at 20 mg/l PAX concentration.................................................................. 84
Figure 4.1.2.4b: The effect of pH and

concentration on the floatability of

synthetic enargite at 20 mgA PAX concentration. ...........................................................

85

Figure 4.1.2.5: The effect of copper sulphate concentration on the floatability of


synthetic enargite at 20 mg11 PAX concentration. ......................................................... 86
Figure 4.1 .2.6: The effect of aeration time on the floatability of
synthetic enargite at 20 mg/l PAX concentration. ...........................................................

87

Figure 4.1 .z.7: Relationship between flotation recovery and pulp potential for synthetic

enargite at pH 9 and 20 mg/l PAX concentration.........................................................

88

Figure 4 - 1 3: Adsorption-flotdon relationship for synthetic enargite............................. 89


Figure 4.1.4a: The effect of xanthate concentration and pH on the contact angle of
synthetic enargite...........................................................................................................

90

Figure 4.1.4b. The effect of pH on the contact angle of synthetic enargite..................... 91

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 4.1.5: Infiared spectra of enargite in the presence ( C w e A) and


.............................. 93
absence (Curve B) of potassium amyl xanthate....................... .
.
.

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 . 1b: Adsorption isothenn for PAX on natural enargite.................................. 121


Figure 5 . 1 . 1 . 1 : The effect of cyanide concentration and contact time on the
pre-adsorbed xanthate on natrirai enargite at pH 9 and 20 mg/l PAX concentration.... 122

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

pre-adsorbed on natural enargite at pH 9 and 20 mg/l PAX concentration.............. 125


Figure 5.1.1.4: The effect of pH on the adsorption density of PAX on naturd enargite. 126
Figure 5.1 -2: Floatability of naturai enargite................................................................ 127
Figure 5.1.2.I : The effect of sodium cyanide concentration and contact time on
the floatability of natural enargite at pH 9 and 20 mgA PAX concentration................... 128

Figure 5.1.2.2:The effect of sodium sulphide concentration and contact time on


the floatability of natural enargite at pH 9 and 20 mg/l PAX concentration.................. 129
Figure 5.1.2.3: The effect of flotation pH on the floatability of natural enargite........... 130
Figure 5.1.2.4a: Floatability of natural enargite as a function of KMnOI
concentration at 20 mg/l P A X concentration................................................................

131

Figure 6.1-2.6: ~elationshipbetween flotation recovery and pulp potentiai for

chalcopyrite at pH 9 and 20 mgii PAX concentration. ................................................. 155


Figure 6.1- 3: Adsorption-notation relationship for chalcopyrite. .................................. 156
Figure 7.2a: The adsorption of PAX on minerals as a function of thle at pH 9

and 20 mgA PAX concentration. .................................................................................. 167


Figure 7.2b: Adsorption isotherms for PAX on minerals at pH 9. ................................ 169
Figure 7.2.1 : The effect of cyanide contact time on the pre-adsorbed xanthate on
minerals at pH 9, 20 mg/'PAX and 15 mg/i NaCN concentration. ................... .
.
..... 1 7 1
Figure 7.2.2: The effect of sodium sulphide contact time on the pre-adsorbed
xanthate on minerals at pH 9, 20 mg/l PAX concentration and
10 mg/l sodium sulphide concentration. .....................................................................

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

Figure 7.3.3: The effect of pH on the floatability of rninerals at 20 mg/l PAX


concentration............................................................................................................... 183
Figure 7.3.4: Floatability of minerals as a function of K M n O d concentration at pH 9
and 20 mg/l PAX concentration. .............................. .
.
.............................................. 185

Figure 7.3.5: The effect of aeration time on the floatability of minerals at


pH 9 and 20 mgA PAX concentration. ..................................... .................................... 1 86
Figure 7.3.6: Relationship between flotation recovery and pulp potential for minerals
at pH 9 and 20 mgA PAX concentration.......................................................................

188

Figure 8.2.3: Copper recovery versus arsenic recovery at 4.75% As in feed sample. .... 198

Figure 9.3. l a: The effect of MAA concentration on adsorption density of xanthate


on minerais at pH 9 and 20 mg/l P A X ......................................................................... 203
Figure 9.3. i b: The effect of pH on the adsorption density of PAX on
minerais at 20 mg/l PAX concentration and 250 mg/l MAA. ........................................ 204
Figure 9.3.2a: The effect of MAA concentration on the floatability of

minerais at pH 9 and 20 mg/' PAX concentration.........................................................

206

Figure 9.3.2b: The effect of pH on the floatability of rninerals


................ 207
at 20 mg/I PAX concentration and 250 mg11 MAA. .......................... .
.
.
.

Figure 9.3.3a: The effect of surface tension regulated by rmthanol on the floatability

of rninerals at pH 9 and 20 mgn PAX concentration..................................................... 209


Figure 9.3.3b: The effect of surface tension regulated by methanol on the floatability
of minerals conditioned with MAA at pH 9 and 20 mgA PAX
concentration............................................................................................................... 2 10
Figure 9.4: Infrared spectra of surface compounds formed on the synthetic enargite
surface afier treatment with MAA................................................................................ 2 15

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

Potassium Amy1 Xanthate

PEX

Potassium Ethyl Xanthate

MAA

Magnesium Chloride, Ammonium Chloride and Ammonium Hydroxide

Min.

Minute

vs.

Versus

Ave.

Average

Conc.

Concentration

Equil.

Equilibrium

Recovery

SCE

Saturated Calomel Electrode

S E

Standard Hydrogen Electrode

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

other copper sulphides. However,

pyrometaiiurgical and

hydrometallurgical techniques for removing arsenic from copper concentrates (Le..


enargite concentrates) have been investigated (Kusik and Nadkarni 1988. Nadkarni and
Kusik 1988).This research reports the results of adsorption. flotation and contact angle

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

particular, an understanding of interaction mechanisms of collectors and depressants with


the mineral surface in an aqueous medium is of cnicial importance in achieving the desired
benefication by Botation. Xanthate adsorption can be studied by a wide variety of
techniques including contact angle, chemicai determinations of adsorption isotherms.
surface potentials and spectrophotometnc methods and valuable data regarding the
orientation of adsorbed xanthates and multi-layer type adsorption could be gained. Since
the adsorption of the collector on the sulphide rnineral surface to render it hydrophobic

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.

2.1 Properties of Xanthate Collectors for Floating Suiphide Minerals

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)

Structurally they may be represented as:

Nonpolar Portion(0rganic Group)k-4

Polar Portion(1norganic Group)

.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 step to xanthic acid in solution as follows:

hydrolysis :

ROCS? + Hz0 H ROCS&I + O H

(2.1.3)

decomposition:

ROCS2H
+
* xanthic acid

(2.1.4)

ROH + CS2
+ aicohol
+ carbon disulphide

Flotation of sulphides using xanthate coiiectors is usuaily conducted in rniidly alkaline


pulps which strongly favours the predominance of the anionic xanthate species in solution.
The highly ionic, alkaii metai xanthates have a solubility of the order of 2-5 moVl (Tiprnan
1970). Potassium xanthates crystallize as anhydrous salts, while the sodium salts have two

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)

3X -i 1/ 2 0 2 -+ HzO --+ Xz+ 20H

(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

appreciable extent in notation systems. It should be mentioned. however, that


electrochemical oxidation of xanthate by oxygen on an appropriate solid surface, such as
pyrite, does occur. With cu2+and ~ e " ,however, the reaction is relatively fast kinetically
(Fuerstenau et al. 1985). Dixanthogen can also be formed homogeneously by oxidizing
agents like KI2 and H202or heterogeneously or electrocatalytically on an electrode surface

(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).

2.2 Mechrnism of Xanthate Adsorption on Sulphide Minerals

Flotation of minerals is govemed by many processes at the soiidniquid/gas interface,


one of which is adsorption of surfactants. This adsorption depends on a number of
parameters such as surface composition of the solid, structure of the surfactant, rnineralsolution equilibrium and the surfactant solution chemistry (Somasundaran and Sivakumar
1988). In general, adsorption fiom solution c m be classified as chemisorption or physical

adsorption. Chemisorption is characterized by high heats of adsorption and by the


complete or partial transfer of an electron or orbital overiap. Physical adsorption is
charactenzed by low heats of adsorption and lack of true bond formation (Rogers 1976).
In chemisorption the adsorbate enters the crystal lattice through chernical reaction at
the inner double layer forming a covalent bond with metai ions in the surface of the
mineral (Fuerstenau and Raghavan 1976). The extent of this depends on the dimensions of
the ions being adsorbed and how closely they approximate to the dimensions of the crystal
lattice ions, on the structure and composition of the rnineral surface layer, and solubility of
the compounds formed. Overall, these factors lead to the high selectivity of chemisorption,
and are of great importance in the action of many reagents for sulphide flotation.

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

Chernical o r Solubility Theory

To explain the rnechanism of xanthate action on suiphde minerais, Taggart et al.


(1934) proposed the chemical theory. They aated that al1 interactions between dotation

reagents and mineral particles consist of weli-recognized types of chemical reactions.


resulting in the creation of definite compounds at the mineral surface. The relative
solubility of these compounds detennines whether or not the reagent is successfl in
creating a hydrophobic surface. This theory assumes that the mineral or an oxidation
product of the mineral occumng at the surface is more soluble than the product formed by
reaction of the minerai surface and collector ions. Taggart's mechanisrn has been shown by
Wark and Cox (1934) to lack general validity since some collector salts are more soluble
than either the mineral or its oxidation product. Another problem with this theory is that it
does not consider the effects of oxygen because recent investigations have shown that this

is a fundamental point in xanthate adsorption.

2.2.2 The Neutra1 iVLolecule Theory

In considering that oxidation of the mineral surface resulted in a large negative


electrical double layer potential, Cook and Nixon (1950) reasoned that adsorption of the

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.

2.2.3 Ion Exchange Theory

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:

2MS + 202 + Hz0 + MS~OI+ M(OEQ2

(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;

SBis the fraction of the surface occupied by sorbed B-ions;


CA and

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)

2.2.4 Electrochernical Mode1 Theory

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.

2.3 Role of Oxygen in Xanthate Adsorption

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

oxygen, and surface oxidation to

s*-, ~ 2 0 3 and
~ -

~0:'

can occur, depending on Eh-pH

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

to penerrate the compact inner layer of the electrical double layer.

2.4 Electricnl Aspects of Xanthate Chemisorption on Sulphide Minerais


2.4.1

Electrical Double Layer

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

solution which results in the formation of an electricai double layer.


In the development of surface charge, the sulphide minerd surface acquires a negative

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

required to bring a unit charge From infinity (L) to a

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

potential is therefore most

important in studies of electrokinetic phenomena.


The zeta potential depends on the surface charge of the particle, and, since it can be

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)

LI = solution viscosity, poise

D = dielectric constant
V = pmicle velociry, c d s e c

E = potential gradient, voltkm

Plane ofs

Figure 2.4.1: The structure and potential gradient of an electrical double layer.

2.41.1

Application to Flotation Systems

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

a controlling factor in flotation.


If the xanthate anion carries a charge -E then it will expenence an additionai potential
bamer in difision to the solid surface of about E W ~(where y. is the negative surface

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

minerasolution interface is of concem. The adsorption density Ts in the plane of shear


.

(F), which is at a distance of closest approach of counter ions to the surtace, 1s gven by
the Stem-Graham equation (Somasundaran 1975):

r6= 2rC e x p [(-AGoa*)lRTJ

(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:

JGoad,= AGocI, + AGoChm+ AG0,, + AGoC,+ A G 0 +


~ AGomo

(2.4.1.1.2)

AGcla is the electrostatic interaction term equai to zFy6 where z is the vaiency of the

adsorbate, F the Faraday constant and

the potential at the plane of shear (6 plane);

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'

interaction between the hydrophobic chah and the

hydrophobie

sites on the mineral

surface; AGoHis due to hydrogen bonding; AGom is due to hydration or dehydration of


the adsorbates or adsorbents upon adsorption. One or more of the above tems cm
predorninate for each system. Spec5c adsorptiori cm be either physical or chemical in
nature. If the ions are adsorbed only through such forces as electrostatic attraction and
rhrough hydrophobic bonding (van der Waals' interaction between hydrocarbon chahs),
the process should be termed physical adsorption. If the coliector forms covalent bonds
with rnetal ions in the surface of the mineral, then the process should be termed
chernisorption. The chemical term is considered to be the predorninant term for the
adsorption of xanthate on sulphide minerais, and the electrical term and the chah-chah
interaction t e n s are important for the adsorption of aikylsuffonates or alkyisulfates on
oxides such as alumina.

2.4.2 Serniconductor/Solution Interface

When xanthate is chemisorbed on a metal sulphide surface to form a metal xanthate


surface compound, an electron transfer must occur. Even in covalent bond fornation an
electron cm be considered removed from the conduction band in the solid and localized in
the chemisorption bond. A knowledge of the electronic structure of the solid adsorbent
may therefore lead to a better understanding of the rnechanisms operative in xanthate
adsorption.

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

band. A term 'serniconductor' is a material having an elearical conductivity intermediate

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.

In semiconductors it is of great importance to recognize two kinds of carriers of


electricai current, electrons and holes. The covalently bonded carbon atoms, in the
diamond modification, are shown in Figure 2.4.2a(a) (Hamy 1968). Since each carbon
contributes four valence electrons, and it is tetrahedrally bonded to four neighbouring

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

is no longer an insulator, but shows appreciable electrical conductivity.

Figure 2.1.2a (Hamy 1968):


(a) Schematic representationof perfect diamond lattice.
(b) Conduction electron in diamond.
(c) Holes in diamond.
(d) Motion of a hole through the diamond lattice.

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.

Figure 2.4.2b: Semiconductor band structure (Poling 1963).

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.

2.5 Electrochemistry of Sulphide Minerals Rotation

In presenting a detailed mechanism of the mineral-collecter-oxygen interaction, it has

&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

sum of the rates of al1 reduction reactions.

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

reactions accompanying, respeaively, loss and gain of electrons.

AU redox reactions can

be split into haif reactions indicating the mode of electron transfer. In general, a half-

reaction rnay be expressed by following equation (Cheng and Iwasaki 1992):


Oxidized State + n Electrons = Reduced State (A" + ne + A")

(2.5.1)

An overall oxidized/reduced state may be represented by the difference in potentials and


expressed by Eh refemng to the Standard Hydrogen Electrode (SHE). The potential of
Reaction (2.5.1) cm therefore, be calculated by the Nernst equation;

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

hydrogen electrode. A lower Eh signifies less oxidizing or more reducing conditions.

The oxidizing or reducing conditions are assumed to be represented by a redox potential.

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

depressants (Chander 1988).


The pulp potential approach is used to study its effect on the flotation of sulphide
rninerals. An electrode pair consisting of an inert electrode and a reference electrode is
widely used to measure redox or pulp potentials. Noble metai electrodes as indicators,

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

state of oxidation of a mineral. AUison et ai. (1972) demonstrated that in xanthate

is fonned when the rest potential is high, metal xanthate (MX)


solutions, dixanthogen (X2)
is fonned when the potential is moderate, and no coiiector species is identified when the

rest potential is low.

2.5.1 Mechanism of Collecter-Induced Notation

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

and electrochemica1 processes.


In the xanthate-induced flotation of sulphide minerals, the cathodic reaction is oxygen
reduction:

1/202+ H20+ 2e- + 20H

(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-

b) Formation of rnetal xanthate

MS + 2X + 4H20 = MX2+ S04' + 8Hf+ 8


C)

(2.5.1.3)

Formation of dixanthogen
3X = X2+ 2e'

(2.5.1.4)

where X represents xanthate ion, and X2 represents dixanthogen.


It is evident that inhibitions of the cathodic reduction of oxygen or the anodic oxidation of

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

an electrochernical mechanisrn (reaction 2.5.1 -4).

2.6 Mechanism of Action of Depressants on Sulphide Minerais

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.

2.6.1 Depression of Sulphide Minerals by Sodium Cyanide

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

conditions. such as pH, concentration and condirioring time, successfl separation of


these rnineral systems c m be achieved.
The depressive action of sodium cyanide is believed to be associated with the ability

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

reactions (2.6.1.1). (2.6.1.2), (2.6.1.3),(2.6.1.4)


and (2.6.1
- 5 ) is rapidly shifted to form

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)

2CN-+ O2+ 2CNO-

(2.6.1.8)

( 0 9 2

+ 1/202+ 20K + CNO- + Hz0

(2.6.1.9)

The oxidation of xanthate to dixanthogen is suppressed because of the large consumption


of oxygen by cyanide. Direct reduction of dixanthogen by cyanide may also occur:

(EX)2 + 2 C N + 2EX + (CN)2

(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).

From a knowledge of the dissociation constant of hydrocyanic acid:

M[Cw/[HCN] = 4 . 7 1~O-''

(2.6.1.1 1)

at 18 O C , the concentration of cyanide ion in a cyanide solution of a particular pH value

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

Depression of Sulphide Minerals by Sodium Sulphide


Sodium sulphide or hydrosulphide has been used in the flotation of mixed sulphide

minerals by xanthate colleaors, either in bulk or in selective flotation. It has a depressing


action on sulphides (like pyrite) in which xanthate acts with its dimer, causing potential to
drift to cathodic values inconvenient for the oxidation of xanthate to dixanthogen

(Fuerstenau et al. 1985).


On dissolving Na2S in water, ionization proceeds in various stages (Crozier 1992);
first:

NazS + 2Hz0+ 2Na- + H2S + 20K

(2.6.2.1)

followed by: H2S + K

+ HS'

where the equilibrium constant is:

K,= M[HSYm2S]= 9.1

x IO-*; p K = 7.04

while the third stage is: HS' + K + S'

(2.6.2.3)
(2.6.2.4)

and the equilibrium constant is:

K2= M [ S = ] / [ H S 1

= 1.1 x

IO-'*; pK= 11.96

(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

Depression of Sulphide Minerals by Oxidation

It seems to be a general characteristics of d dphide minerals that they cannot be


floatable d e r serious oxidation (Guongming and Hongen 1989). In an aqueous solution,
the surface of oxidized wlphide minerals usuaiiy consist of the metal oxides, hydroxides
and oxysulphides.

AU these species are hydrophilic. However, if elementai sulphur or a

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

power of the permanganate, depending on the conditions. The characteristic reduction


reactions of permanganate are:
pH 5:
Mn7*+ Se o iMn2-

2MnOi + Hz0

t,2MnO

+ 20K + 5/202

pH 7:
Mn7-+3e t t M n 4 -

2MnOL + H20 t,2WO2 + 20K + 3/O2


pH 9:
Mn7'+ e tt h4n6+

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.

2.7 Contact Angle Studies of Sulphide Minerals


Froth flotation involves the aggregation of air bubbies and minera1 particles in an
aqueous medium with'subsequent levitation of the aggregates to the surface and transfer

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

gas as shown in Figure 2.7.

Figure 2.7: Schernatic representation of equilibriurn contact between


an air bubbIe and a solid irnmersed in a liquid (Fuemenau
et al. 1985).

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:

AG = YSG - (YSL + YLG)

(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

minimum, indicating that the surfactant

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

minerai (Gaudin 1957), however, no d e f i t e relationship has been obtained. in fact


successful sulphide mineral recovery by flotation requires that the arnount of collector
present be considerably less than a monolayer of colector, while stable contact angles are
measured when there are multilayers on the sarnple surface (Croier 1992). At present, it
is only possible to Say that a finite contact is a pre-requisite to flotation. It has been
established that the maximum contact angle is independent of the mineral. and oniy a
function of the collector (Sutherland and Wark 1955). For example, in the xanthate-

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

and clean if reproducibility is to be obtained. Theoreticaily the minerai surface is

considered to be perfectly flat, however, this is practicaily impossible, as micro-crystalline


cracks wiii be present no matter how carefiil the polishing. This results in variations of the
contact angle. To overcome this, the contact angle must be measured at ditrerent spots on
the mineral surface, and the average taken as the tme angle.

2.8 hfrared Surface Studies of Sulphide Minerals

Many spectroscopic techniques can be employed to study the physicochemical


interfacial phenornena of importance in mineral processing. These techniques are
extremely usefl in characterizhg the solid surfaces and in understanding the reactions at
the so1idAiquid interface (Somasundaran and Sivakumar 1988). This review discusses the

application of the inftared spectroscopy technique. Mared spectroscopy is employed to


study the structure of molecules (Marabini et al. 1993). Since an infiared spectrum

presents an analysis of the vibrational modes in molecules it cm ofien be the most


characteristic single feature of a molecule. It permits identification of substances fiom the
chemicaf crystalline aspects. The infiared investigation of xanthate adsorption on sulphides

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

reflection-absorption techniques. Infiared spectroscopy can be performed in transmission,


reflection and emission modes.

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.

In studying adsorption of xanthates on sulphide minerais by hf?ared spectroscopy, it


becomes necessary to assign the spectral fiequencies to the vibrational modes of the
xanthate group (Little et al. 1961). Little et ai. assign the band at 1020 to 1070 cm-'to the
stretching mode, C=S. The bands at 1200 and 1110-1140 cm-'are assigneci to the C-O-C
stretching vibration. However, for dixanthogen, the stretching mode of C=S is retained at
1020 to 1070 cm-', the C-O-C stretching mode is shifted to 1250 cm", and the other band

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-'.

2.9 Critical Surface Tension of Wetting

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

fiaction of a component of surface tension y', and (LX)mole fraction of a second


component of surface tension y2 (Osipow 1977). The concept of critical surface tension of
wetting, y., developed by Zisman (1964), correlates the Iiquid/vapour-interfacial of ylv of a
liquid with contact angle 9 and is defined as the ylvat which CosB=l.

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,/,.

When a solute is weakiy surface active at the aidwater interface, it

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!

Under such conditions. solid B is completely wetted (8=0),while solid

characterized by @O0, floats (Laskowski 1986).

2.10 Mineral Characterization

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.

Figure 2.10.la: Enargite composition in the Cu-As-S system in atom


percentage (Maske and Skinner 1977).

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.

Figure 2.1 O.1b: Crystal m c m of enargite (Gajam and Raghavan 1983 1.

Enargte is found in hydrothermal vein deposits formed at moderate temperatures and

aiso it is a Iate-stage mineral in low-temperature deposits (Anthony et al. 1WU). Enargite.


found at Butte, Chuquicamata and Cerro de Pasco, is a usual minerai in porphyry copper
deposits (Perez-Segua and Zendejas-Mendivil 1991). It is a widespread minerai. Found in
the US4 in splendent cryaals from Butte, Silver Bow Co., Montana; in Utah, in the
Tintic district. Tooele Co.; in Colorado. in fine specimens from a number of mines in the

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).

Enargite is a semicondudor with an energy gap of about 1 eV. It is always p-type,


apparently due to a sulphur excess of over 0.1%. While the hole concentration at room
temperature is quite large, around loZ0cmJ, the resistivity is not very low, only on the
order of 10" ohm-m.Thus the hole mobility is quite low. around 0.1 ~rn~v"sec'~
at room
temperature. From the tetrahedral CO-ordinationone expects covalent bonding and hence
delocalkation of holes (Shuey 1975).

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.

Figure 2.10.2a: Chalcopyrite composition in the Cu-Fe-S system (Shuey 1975).

It belongs to the tetragonal crystal

system. In the stmchire, each sulphur is tetrahedrally

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.

Figure 2.10.2b: Crystai shucture of chaicopyrite (Crotier 1992).

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

compounds and polishing powders.

3.1 Materials and Equipment

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

sample. However, no other rninerals were observed in synthetic enargite. Luzonite

the low temperature polyrnorph of enargite, appears to be similar to enargite in


(CU~ASS~),
formula, but is distinguished fiom enargite by its orange-yellow colour and lamellar twins
(Craig and Vaughan 198 1). Moreover, the inversion temperature of luzonite to enargite is
300 O

(Maske and Skinner 1977).

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

Specific Surface Area in m2/g


-

-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

Lambda 38 WMS Spectrophotometer at 301 nm (Appendix A2). Analytical g a d e


sodium hydroxide and hydrochlonc acid were used as pH regdators, sodium sulphide.
sodium cyanide and potassium permanganate as depressants, and copper sulphate as an
activator, were used when required in al1 testwork. Required solutions of each reagent
were prepared fiesh prior to the tests. Distilled water was used to prepare different
solutions throughout the entire midy. The standard tests were performed at pH 9.0 using

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

adsorption or notation recovery. AU tests were conducted at room temperarure (2322OC).


in order to eliminate possible contamination especiaiiy by dixanthatogen, aU glassware was
washed thoroughly in dichromic acid solution and then in hot water and d k d ovemight at
120 OC.

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

ml tube of freshly prepared xanthate solution at a predetermined concentration and pH


value, which was completely filled to eliminate air bubbles. Agitation was provideci by
rotating on a mechanical device at 30 r.p.m. At the end of adsorption, the tube was
centrifged to settle the suspended minerai particles and the clear Iiquid was used to
detemine the final concentration of the collector. The initial and final xanthate
concentrations were determined on the UV S pectrophotometer with the difference
representing the amount of collector adsorbed.

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

equilibriurn xanthate concentration in the Tables presented in Appendix Ag.

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

of pH 9 d e r which it was conditioned for 20 minutes. Finally, electrochemical pre-

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.

Details of data are presented in Appendk A9.

3.2.3 Contact Angle Measurements

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

Infrared Absorption Study

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.

3.2.6 Zero Point-of-Charge Measurements

The zero point-of-charge ( q c ) of synthetic enargite was determined using the


adsorption of potential determining ions technique. A mixture of 400 ml of 0.1 Normal
Potassium Chloride (KCI) and 1.181 ml of sodium hydroxide was used as an electrolyte.
Four gram of enargite sample were added to the solution. Agitation was performed using

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.

3.2.7 Rest Potential Study

The most common arrangement to study the electrochernicai property of a sulphide


mineral is to make the minerai Uito an electrode that is usuaily called the working
electrode. The potentid of the electrode is measured with respect to a saturated calomel
electrode as a reference electrode. It is a common practice to report the measured
potentials on the hydrogen scaie by adding 0.242 V to the potentials measured with
respect to the saturated calomel electrode. The rest potential of an enargite electrode fier

10 minutes in a 6 . 2 5 ~ 1 0M~ solution of potassium amyl xanthate having a pH value of 7.

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

initial xanthate concentrations. The adsorption of xanthate on synthetic enargite reached a

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.

The adsorption isotherm of xanthate on the synthetic enargite surface at pH 9 is


presented in Figure 4.1.1b. This isothenn exhibits a curve of L (Langmuir) type for which
adsorption slows down as it proceeds.

+Adsorption

iaothtrm

-C- D e s o r p t i o n isothcrm

0.1

:
0.1

, , ,

10

IO0

Equilibrium Xanthate C oncentration ( m g / l )

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:

r = xanthate adsorption density (mgIn?)


C = equilibrium xanthate concentration (mgIl)
k and n are constants.

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.

The Langmuir relation is &en by:

r=(~crj(
I +qc)

(4.1.1.2)

where:

r = xanthate adsorption density (mg/m2)

ro= adsorption density corresponding to a monolayer


C = equilibrium xanthate concentration (mgh)

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

Equilibrium Xanthate Concentration (mgli)

Figure 4.1. lc: Langmuir plot of C K versus C for the adsorption of xanthate
on synthetic enargite.

Of particular interest in collector adsorption is the concept of monolayer coverage.


Monolayer coverage represents the saturation of al1 of the available sites on the mineral
surface by the collector. However, in many cases the plateau cm happen at adsorption
densities which are far from the calculated monolayer coverage due to different

orientations of colieaor coverage and physicai adsorption of additional layers of xanthate


on the initiai chemisorbed layer. Taking the cross-sectional area of the xanthate molecules

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

Effect of Sodium Cyanide on Adsorption

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

Effect of Sodium Sulphide on Adsorption

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

mg/i sodium sulphide concentration it decreases to 50 percent of the original adsorption


density. At 20 minutes contact tirne the adsorption density is 75.2, 42.6 and 30.5 percent

of their original values at 5, 10 and 15 mg/l sodium sulphide concentrations, respectively.

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

original adsorption density.


It is obvious that the pre-conditioning of the mineral with sodium sulphide followed

by xanthate addition has a lower effect on the reduction of xanthate adsorption than on the

reverse reagent addition sequence.

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

Effeet of KMn04 on Adsorption

Figure 4.1.1.3 shows the effect of the

K m 4

concentration and the contact tirne on

the pre-adsorbed xanthate. The results show that as the -O4

contact thne increases to

60 seconds, a rapid desorption of xanthate occurs, and then there is a readsorption of

xanthate on the synthetic enargite surface. At 10 mgil KM.04 concentration readsorption

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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CI

<

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;...:.......-.-.........
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..................
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.
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4 .

..

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.:.
.,........
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....;..............
.. .. ..
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10

15

..

.
..
..
.
.
.
Ah
. . . ............
.

.
..

..

..

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

KMnOJ solution. At 20 mgA xanthate concentration the adsorption density is 57 percent of


the onginal adsorption density.
The above results show that for 10 minutes KMn04 contact t h e , its effect is higher

on the pre-adsorbed xanthate on the minera1 surface than on the reverse reagent addition
sequence.

4.1. t .4

Effect of Copper Sulphate on Adsorption

The effect of copper sulphate concentration on adsorption density of xanthate on


synthetic enargite was evaluated. Figure 4.1.1.4 shows that copper sulphate increases the
adsorption density of PAX on synthetic enargite. The effect is not remarkable at 10 mg/l
copper sulphate concentration. The results indicate that, by conditioning the synthetic
enargite surface with 25 mg/l copper sulphate, a higher adsorption density is obtained as
compared with the adsorption isotherm without the copper sulphate addition as s h o w in
Figure 4.1.1.b. This isothenn indicates an H type curve, a modified L curve which

represents a higher affinity compared to L type curve.

0.1

+Copper Sulphate Conc.=1O mgA

1O

1O0

Equilibriurn Xanthare Concentration ( m e )

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.

Additional information on the adsorption mechanism is derived by studying the effect

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.

........... ........................*... ...........


.
t

-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.

4.1.1.6 Effeet of Aeration on Adsorption

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

concentration of 30 mg4 PAX.

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.

The effect of coiiector concentration at the same pH on the flotation of synthetic


enargite using potassium ethyl xanthate is also presented in Figure 4.1.2. The results show
that the coilector effectiveness increases with increasing alkyl length of xanthate up to a

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

Effect of Sodium Cyanide on Rotation

The effect of sodium cyanide concentration on the flotation recovery of synthetic


enargite pre-adsorbed with xanthate is presented in Figure 4.1.2.l a The depression rate.
the extent of depression, and the final recovery values are strongly influenced by the

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

higher cyanide concentrations. The depression, however, loses its

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

Sodium Cyanide Contact Time ( m i n u t e s )

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

synthetic enargite decreased to 21 percent (Table 4.2).

Table 4.2: The &ett of deprsants on the synthetic enargite flotability.

Test Conditions
Initiai PAX Conc.=2O.O mgi. Conditionkg Tirne= 10 min.. pH=9.0

1 Original 1
71.95

First Conditioned With Depressant


Naz& 10 mg/i
KMri04.50 mg/l
-

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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.. .. .. ..........
. --*----.... . . .-----._... .. .._.-..
. ..-.....
-..--.-...--....-.-..--..~.-~--..-..---.-*~~.---...*
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..
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- --..-.......-...-..-.;....;..-&...;....;.-..:....;...; ....:-...;....;...; .....
.. .. .. ...--...-.. .. ..-.--;
.. .. .. .. .. .. .. .. .. .. .. .. ..
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..

..

..
.

..
.

..

Sodium C yanide Contact T i m e Cm inutes)

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

Sodium Cyanide Contact T i m e (minutes)

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.

4.1.2.2 Effect of Sodium Sulphide on Rotation

The effect of sodium sulphide concentration on the synthetic enargite flotation

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

concentrations of 5, 10 and 15 mg/l, respectively. After 5 minutes, the synthetic enargite


flotation decreased much more slowly.

.
.

..
.

..
.

..

..

..

..

..

..

..

..

..

..

..

..

..

..

...

...

..

..

.__._...__..._.
-+
.. - 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.

As synthetic enargite was conditioned with sodium sulphide followed by xanthate


addition, the flotation recovery was 55.6 percent at I O m g sodium sulphide concentration

for 10 minutes conditioning with sodium sulphide. The result is shown in Table 4.2.

4.1.2.3 Effects of pH and pH Regulators on Fiotation

Figure 4.1.2.3a shows that a neutral solution to pH 1 1 has little effect on the

floatability of synthetic enargite. At a pH higher than 1 1 , the flotation is greatly reduced.


The pH adjustment by Ca0 was also investigated. A s m d decrease was observed in
recovery when using Ca0 as pH regulator as compared with NaOH.

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 .

Figure 4.1.Z.3 b shows a decrease in xanthate concentration fiom 20 mg11 to 10 rngA


resulted in a decrease in the synthetic enargite recovery. The decrease in recovery is about

5-33 percent fiom pH 6 to pH 1 1, but at pH 12 the flotation recovery is very close for both
xanthate concentrations.

Figue 4.1.2.3b: The effect of flotation pH and PAX concentration on the


floatability of synthetic enargite.

4.1.2.4

Effect of KMnOl on Notation

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

Figure 4.1.2.4a: Floatability of spthetic enargite as a fiinction of KMnOj concentration


at 20 rngn PAX concentration.

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

enargite depression is presented in Figure 4.1.2.4bwhich shows a small decrease in

flotation recovery to pH 9. As the pH increases to 12, the synthetic enargite recovery is


nirther decreased to 10-45 percent dependmg on the KMnOj concentration.

Figure 4.1.2.4b: The &ect of pH and KMn04concentration on the floatabiIity of


synthetic enargite at 20 mg/PAX concentration.

4.1.2.5

Effect of Copper Sulphate on Flotation

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

copper sulphate concentration of 25 rng/l. Above 25 r n d there is a decrease in notation


recovery.

1O

iO0

C o p p e r Sulphatc Concentration ( m g / l )

Figure 4.1-2.5: The d c t of copper sulphate concentration on the floatabiliiy of


synthetic enargite at 20 mg/l PAX concentration.

4.1.2.6

Effect o f Aeration on Flotation

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)

Figure 4.1.2.6: The eEect of aeration conditioning on the floatability of


synthetic enargite at 20 mgn PAX concentration.

4.1.2.7

Effect of Pulp Potentials on Rotation

To investigate the eEect of pulp potentials on the floatability of synthetic enargite.


and to explore the possibility of monitoring or controlling the potential for depression of

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.

-600 -500 -400 -300 -200 -100 O


Potcntial (m V v s . SC E)

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

The adsorption-notation relationship for synthetic enargite is presented in Figure


4.1.3. The results were obtahed at pH 9.

This relationship shows that there is a sharp

increase in synthetic enargite recovery up to 2 mg/m2 adsorption density. As the


adsorption density is increases nom 2 mg/m2 to 4 mg/m2 there is a 6.35 percent increase in
recovery. The adsorption density of 4 m g / d is a critical point, indicating a synthetic
enargte recovery of 74.95 percent. This point corresponds to a 20 mgIl initial xanthate

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)

Figure 4.1.3: Adsorption-flotation relationship for synthetic enargite.

4.1.4 Contact Angle of Synthetic Enargite

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

pH 1 1 as compared with that of pH 6 and pH 9.

10

20

30

40

50

Xanthate Concentration (rng/l)

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

P.4.Y Conc.=SO mgIl

+ PAX Conc.=20 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

NaC N Concentration (mg/[)

Figure 4.1.4~:The effect of NaCN concentration on the contact angle of synthetic


enargite at 20 mg/l PAX concentration.

4.1.5

Infrared Absorption Spectra of Synthetic Enargite

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.

4.1.6 Solubility of Synthetic Enargite

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)

Aeration Time (min.)

Cu (m@)

As (md)

4.1.7 Zero Point-of-Charge of Synthetic Enargite

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

using this method was detennined to be 3.

Figure 4.1.7: Detennination of zero point of charge of synthetic enargite using the
adsorption of potential determinhg ions technique.

4.1.8 Rest Potential of Synthetic Enargite

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:

(X)2 + te' o 2)C

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.

SHE.The equilibrium potential of dixanthogen/xanthate for ethyl xanthate

(EO= -0.060 V) was calculated to be 0.130 V vs. SHE. There was a dinerence of 90 m V

between the rest potentids for ethyl and amyl xanthate.

4.2 Discussion
4.2.1

Adsorption

In order to understand the fndamental flotation mechanisms of enargite, it is


necessary to study the adsorption of xanthate ont0 the surface of the mineral because the
flotation behaviour of nilphide minerals depends on the adsorbed species present on the
rnineral surface. Therefore, characterization of the interaction mechanisms between the
aqueous solution of potassium amyl xanthate and synthetic enargite was carried out by
adsorption studies.
Xanthates are assumed to adsorb on sulphide rnineral surfaces due to chernical forces
between the polar group and the surface, resulting in insoluble metal xanthates, which are
strongly hydrophobic. Mechanisms involving the formation and adsorption of
dixanthogen, xanthic acid, etc., have also been proposed. It has been established that the
sulphide is not joined to the coiieaor anions without the previous action of oxygen.
Adsorption of collecter bas long been believed to involve an ion exchange mechanism as
demonstrated for chalcocite (Gaudin and Schuhrnann 1936) and galena (Mellgren and
Subba Rau 1963). It is recognized that dunng the chernical interaction between a reagent
and a mineral, the reagent has to difise to the solid surface through the relatively
immobile layer of Iiquid surrounding the mineral particles. Approaching the minerai
surface the reagent ions may exchange with ions fiom the mineral surface forming monomolecular or multi-rnolecular layers of interaction products on the mineral surface. In the
latter case (at high consumption) the interaction products interfere with frther penetration
of reagent ions to the mineral surface and therefore the adsorption rate will depend on the

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

enargite is a complex rnechanism of chernical nature. The adsorption of xanthate on


enargite is aEected by a number of chernical factors including collector concentration and
the surface chemistry of enargite in xanthate solution Le., oxidation products on the
surface of enargite. The inflection or plateau in the observed isotherm suggests an initial
chemisorbed layer is formed on the enargite surface followed by physicai adsorption of
additional layers of xanthate. Initialiy the adsorption density nses steeply as the
equilibnum concentration increases, reaching a value of 3 -991 mg/m2 at an equilibrium
xanthate level of 1.22 mgll. According to the ion exchange rnechanism of adsorption, there
is no diffusion problem in this region and the reaction rate is controlled by the difision of

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.

showed the charactenstic peaks for diisopropyl dixanthogen. However, the

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

potential of the dixanthogedxanthatecouple.

In order to research the hydrophobic species responsible for enargite flotation,


infiared adsorption, mineral solubility and rest potential studies were conduaed. The
results show that the synthetic enargite solubility is low (Table 4.3) as compared with
chalcopyrite at the same conditions (Ackerman et al. 1987). It has the rest potential of less
than the equiiibriurn potential of the dixanthogedxanthate couple and the principal bands

of cuprous xanthate exkt in IR spectra (Figure 4.1.5). Enargite is a p-type semiconductor


(Shuey 1975). As a result, based on the electronic structure of the mineral, mineral
solubility, electrochemical mode1 theory and infiared spectra it is suggested that cuprous
xanthate is the principal hydrophobic species for enargite.

42.2 Flotation

Surface phenomena that reflect conditions at the soiid-liquid interface (adsorption


density) can be correlated directly with surface phenomena that reflect conditions at the
solid-liquid-gas interfaces (flotation and contact angle). The floatability of a mineral is
afTected by many variables, Le., particle size. xanthate concentration, pH. conditioning
time and flotation time. In a preliminary investigation, the effeas of these variables were
studied, and the standard conditions were selected for frther tests. The standard
conditions have been descnbed in previous chapters. Figure 4.1.2 shows the relationship
between collecter concentration and flotation of synthetic enargite at pH 9. This
relationship is a parabolic one with higher increase at low concentrations and a gradua1

asymptotic approach at higher values of xanthate concentration. There is a colleaor


concentration of 20 mg/l above which there is no significant increase in flotation recovery.
The synthetic enargite adsorption-notation relationship shows a critical adsorption density

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

Effect of Sodium Cyanide

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

formation of strong copper-cyanide complexes selectively dissolves cuprous xanthate. In


alkali solutions copper ions d l readily combine with free cyanide to form highly soluble
complexes. It is generdy accepted that three complexes may be present, as discussed in
Chapter 2, and the ratio of these complexes is dependent on the initiai cyanide ion
concentration. The reaction of cuprous xanthate and free cyanide is suggested as foIlows:
C U Z X+~8 C N + ~CU(CN)~.+
2X

(4.2.3.1)

The complex Cu(CN)JS is the final complex. Wark and Cox (1934) caicuiated the free

cyanide concentration at pH 9 to be 17.0 mg per 100 mg NaCN added. According to their


data the concentration of fkee cyanide at this pH for 15 mgA sodium cyanide applied in this

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

in enargite flotation can generdy be considered as the depression of enargite. Glembotskii


(1972) reported that arsenic xanthates are insoluble in cyanide solutions. It forms neither

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

adsorption of xanthate on ternantite (CUI~AS&) by Mielczarski et a1 (1995) also showed


that only cuprous xanthate was present on the surface of this copper arsenic rnineral.
Another important point, however, is the enargite-cyanide interaction. The
consumption of free cyanide ions bnngs about the dissolution of enargite to form soluble
copper cyanide complexes, the complex Cu(CN)Im being the predominant species. Thus
the role of cyanide, when employed as a depressing agent before application of xanthate
on synthetic enargite is to leach out copper ions and to reduce the xanthate adsorption.

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

increase in xanthate concentration retards the rate of maximum depression to 5 minutes.


This is because there is an increased amount of precipitated cuprous xanthate which must
be removed prior to direct attack of the synthetic enargite siuface by cyanide.
Decreasing the particle size Uicreases the flotation recoveiy for a k e d P A X
concentration at any NaCN concentration (Figure 4.1-2.1c). This is because there is an
increase in surface area of synthetic enargite. Considering Figure 4.1.2. l b, showing the
effect of xanthate concentration, this type of behaviour rnight be expeded, since an
increase in surface area corresponds to a decrease in xanthate concentration. The
approximately the same flotation recovery values for both particle sizes after 20 minutes
suggests that the final recovery is dependent only on the cyanide concentration.

42.4 Effect of Sodium Sulphide

The application of sodium sulphide as a depressant for synthetic enargite was


evaluated. Figure 4.1.1.2 shows the influence of sodium sulphide concentration and
contact time. It was found that by increasing the contact time, the adsorption density
decreased. The desorption of xanthate Yom the enargite surface by sodium sulphide can
be explained by a chernical displacement mechanism (Leja 1982). The sulphide ions

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

potentiais, therefore, the mechanism of sodium sulphide depression on synthetic enargite is


not due prirnarily to its reducing property.

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

Effect of Copper Sulphate

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).

As observed in flotation tests, with an increase in pH there is a small decrease in

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

decrease in recovery at pH 11 is due to the decomposition of the colleaor and the


formation of hydrophilic metal hydroxides on the synthetic enargite surface. With regard
to the effect of pH regdators, lime exerts some decrease in recovery. The depressive
action of lime on synthetic enargite is probably due to the fixation of ca2' on its surface
and the formation of the hydrophilic compound CaS04.2H2O (Fuerstenau et al. 1968).

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.

42.9 Effect of Pulp Potentials

The developrnent of hydrophobicity by sulphide mineral particles in a notation systern


arises from an anodic process involving the coiiector which is coupled to

a cathodic

process, generally the reduction of oxygen:


1/202+ H20+ 2e'

+ 20H'

The pertinent anodiz processes are:

charge transfer chemisorption of a thiol ion (X):


XI-+ Xads+eandior: oxidation-of the thiol to its disulphide:
2X'

-+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.,

2MS + 4X + 3H20-,2MX2 + s203"+6K + 8 5

(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

oxidation of the minerd surface:


MS + 2H20 + M(0H)z + S + 2lT + 2

(4.2.9.6)

and, when the collecter is added, a methatical reaction couid take place,

M(OWt + 2X -t MX2 + 20K

(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

the electrochemical process (Woods and Richardson 1986).


The rates of the individual processes responsible for establishg a hydrophobic
sufice Vary with the magnitude of the potential across the mineraVsolution interface and
hence the electrochernical mode1 implies that flotation recovery will be a function of the
potential.
There are in principle two possibilities of varying the redox conditions of sulphide
flotation. These are. firstly. application of chemical reducing and oxidizing reagents such

as sodium sulphide, potassium permanganate. bichromate. etc.; dotation in an atmosphere


of inert gas. or saturation of the pulp with oxygen; and, secondly, direct specific variation

of the potentiai of semiconducting minerals by means of their electrochernicai charging


(Chanturiya and Vigdergau 1989).
The potential of a synthetic enargite-saturated calomel pair inserted into the

electrochemical-microflotation ce11 was measured and controlled by the addition of


oxidant or reductant. It is clear from Figure 4.1.2.7 that Eh controlled the enargite

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

the collecter with one of the products of s d a c e oxidation.


It is suggested that the hydrophobic entity for enargite is cuprous xanthate produced
by a reaction of the following f o m (Hepel and Pornianowski 1977):

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

Contact Angle of Synthetic Enargite

Contact angle is a definite and real physical quantity characteristic of a three-phase


system. Conventionaily, it is meamred within the liquid, and it is the angle between the
liquid-solid surface and the liquid-gas surface. It is obvious that there must be a
relationship bebveen the magnitude of the contact angle and the density of the adsorbed
coating of a surface-active substance. Contact angle studies show that a relatively
maximum contact angle is reached at xanthate concentrations of above 20 mg/l which is in
good agreement with the concentration at which maximum adsorption density appears on
the synthetic enargite adsorption curve. It is known that elemental sulphur is higldy water
repelient, and very easily floated without the aid of a collecter. Synthetic enargite in pure
water gave a very small contact angle, but in a solution of xanthate with concentrations of
20 mg/l or more, the contact angle was 74-80.4O. It is therefore proposed that the surface

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

Infrared Absorption Study

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

Solubility of Synthetic Enargite

In their work Ackerman et al. (1987) have shown that the solubility of 'UC

fkom the

copper sulphide minerals foilows the foilowing sequence:


coveilite > chalcopyrite chalcocite z bornite
These cations released fiom the surface would be avdable to cause: abstraction of
xanthate by produchg metal xanthate on the minerai surface, precipitation of the metal
ion hydroxide in solution or

on the mineral surface, or oxidation of xanthate to

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).

4.2.13 Zero Point of Charge of Synthetic Enargite

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

Rest Potential Studies

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

xanthate reacts chemically with copper ions, obtained fiom the

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

of copper sulphide causes the adsorption density of synthetic enargite to be increased


substantially.

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

maximum contact angle of 80.4' was obtained at a xanthate concentration of 50 mgl.


The addition of depressants brought about a rapid desorption of xanthate from the
synthetic enargite surface. The increase in notation recovery at 15 mg/l cyanide
concentration was only 9.9 percent &er 20 minutes. Sodium sulphide decreased the
flotation recovery by increasing the contact time. Synthetic enargite was also depressed by
the application of potassium permanganate. The efFect of these depressants on the pre-

adsorbed xanthate was in the order of


sodium cyanide > potassium permanganate > sodium sulphide.
The effect of depressants on the adsorption density which was evaluated by the preconditioning of synthetic enargite in a depressant solution is also in the same order. The
flotation results suggest that synthetic enargite will not stay floatable under oxidizing
conditions.

Determination of infkared absorption spectra, mineral soiubility, zero point of


charge and rest potential for synthetic enargite was canied out and correiated with the
adsorption and flotation results.

CHAPTER 5
Flotation Chemistry of Naturai Enargite

5.1 Resuits
5.1.1

Adsorption

The investigation of adsorption kinetics for a potassium arnyl xanthate concentration


of 20 mg/i at pH 9 showed that the adsorption of xanthate on natural enargite reaches
completion within 60 minutes as s h o w in Figure 5.1. l a The xanthate uptake was very

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.

The adsorption isotherm of xanthate on n a d enargite d a c e in an aqueous

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

enargite increases rapidly, a Freuniich type isothem, indicating a high abstraction of


.

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

Equilibnum Xanthate Concentration (mgl)

Figure 5.1.1 b: Adsorption isotherm for PAX on natural enargite.

Effect of Sodium Cyanide on Adsorption

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,

and the mthate adsorption

density recovers to 65 percent of its onginai value in 20 minutes. At 10 mgIl cyanide


concentration, readsorption of xanthate commences at 120 seconds but the adsorption
density climbs back very slowly and never recovers to its original value.

-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

Cyanidc Contact Tim c (minutes)

Figure 5.1.1.1 : The &t


of cyanide concentration and contact tirne on the pre-adsorbeci
.uanthate on nantral enargite at pH 9 and 20 rn@ PAX concentration.

me effect of sodium cyanide, evaiuated by conditioning the naturai enargite sample


with cyanide foilowed by adding xanthate, is given in Table 5.1. The adsorption densisr at
20 mg/l xanthate concentration is 69.2 percent of the on@

adsorption density.

Table 5.1 : The effect of depressants on the xanthate adsorption on n a t d enargite.

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

Effect of Sodium Sulphide on Adsorption

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

Effect of KMnOd on Adsorption

Figure 5.1.1.3 shows the effect of -4

concentration and contact time on the pre-

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

minutes contact at a concentration of 50 mgIl KMn04 the adsorption density recovers to


57 percent of the origina adsorption density.

..

..

......

..

K M n O , C o n c . = 2 5 rn g/l
C o n c . = 5 0 mg/]

+K M n O ,

K M n 0 4 Contact Timc (minutes)

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

The relationship between pH and the adsorption density of xanthate is presented in

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.

5.l.l.S Effect of Aeration on Adsorption

The effect of aeration on the xanthate ads

esented in Table 5.1. The

adsorption density d e r 20 minutes aeration is 67.4 percent of the original adsorption

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

Original Xanthate Concentration (mg/l)

Figure 5.1.2: Fioatability of naturaI enargite.

5.1.2.1

Effect of Sodium Cyanide on Flotation

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

Sodium Cyanidc Contact Time (minutes)

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.

The effect of sodium cyanide o n the naturai enargite flotation, evduated by


conditioning the mineral sample in 15 rngA sodium cyanide solution followed by xanthate
addition and flotation, shows that the flotation recovery decreased to 47.75 percent (Table
5.2).

Table 5.2: The &kt of depressants on the natural enargite floatabiliry.

Test Conditions

initial PAX Conc.=20.0 m f i Conditionhg Tirne40 m h , pH=9.0

%R
Onginal

NaCN. 15
71.25

5.1.2.2

F'irst Condltioned With Depressant

ma

Na2S. IO mgA

KMn04.50 mR/1

Aeratioe 20 mia

57.83

47.35

5 1.25

47.75

Effeet of Sodium Sulphide on Flotation

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

..

..

Sodium S ulphidc Contact Tim c (minutes)

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

flotation. As is s h o w in Table 5.2 the notation recovery is 57.83 percent at 10 mg/l


sodium sulphide concentration.

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

recovered at pH 1 1 and 12, respectively.

- ........ -- P A X C o n c . = 2 O m g l l
I

...................-.......................
I

Figure 5.1.2.3: The effect of flotation pH on the floatability of natural enargite.

5.1.2.4

Effect of KMn04on notation

A study was conducted on the depressing a d o n of potassium pemianganate on the

flotation of naturd enargite at pH 9. The concentration of coilector was maintained at 20

m g . It is obvious that the natural enargite floatability depends on permanganate


concentration as is shown in Figure S. 1 ..k From 0.1 mg/l to 10 mg4 KMnOl the
recovery of natural enargite decreased slightly from 71 to 69 percent. As the KMnOJ
concentration increased frther, the depression extent of natural enargite is greatly
increased. Recovenes of about 43 and 30 percent were obtained with 50 mg/i and 100
m g KMnOJ,respectively.

0.1

10

K M n 0 4 Concentration ( m g I l )

Figure 5.1.2.Ja: Floatabiliv of naturai enargite as a function of KMnOs


concentration at 20 mg/l PAX concentration.

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

notation recovery is atained.


The effct of permanganate on the floatability of naturai enargite was also studied at
pH values of 6 and 12. The results of these tests are presented in Figure S. 1.2.4b.where
recovery is ploaed against pH at the KMnOI concentration of 100 mgil. As cm be noted

there is no change in flotation recovery nom pH 6 to pH 9.However, a strong decrease in

floatability is observed at high aikaline pH values, Le., 13 percent of enargite is recovered


at pH 12.

Figure 5.1.2.Jb: The eff' of pH and KMn04 concentration on the floatability of


naturai enargite at 20 mgR PAX concentration.

5.1.2.5

Effect of Aeration on FIotation

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

Aeration Tirne (minutes)

Figure 5-1.2.5: The &'of aeration on the fioatability of n a d enargite


at 20 mg/l PAX concentration.

5.1.2.6

Effect of Pulp Potentials on Flotation

The intluence of the electrochemical potentiai on the floatability of natural enargite

was investigated. Flotation tests camied out in a microflotation-electrochemicai ceIl


demonstrated that the nahiral enargite flotation is strongly dependent on potential. The
generai trend indicates that nanirai enargite is depressed at reducing potentials, and floated

at moderately oxidizing potentials. Once rendered

floatable by moderate oxidadon, it can

be depressed by increasing the potentid to oxidi;ring values as shown in Figure S . 1.2.6.It


is clear nom this figure that Eh controiied the naturai enargite floatability. Floatability was
reduced at Eh values below -245 mV vs. SCE, but achieved maximum d u e s at the Eh
ranges between -245 and +14 mV vs. SCE at 20 mg/' PAX . At Eh values higher than +14

mV the floatability again decreased as the concentration of potassium permanganate was


increased.

-500 -400 -300 -200 - 1 00

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

PAX concentration, the fioatability is 83.O percent.

A d s o r p t i o n D e n s i t y (rn gfrn ')

Figure 5.1.3 : Adsorption-flotation relationship for naturai enargite.

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.

The rate of xanthate adsorption on natual enargite can be explaineci in terrns of an


ion exchange mechanism. Lnitially the adsorption density rises steeply as the equilibrium
concentration increases, reaching a value of 7.484 mg/m2 at an equilibrium xanthate level
of 1 mg/L In this region the reacton rate is controlled by the diffusion of copper ions fkom
the natural enargite surface. Between the equilibriurn concentrations of 1 and 18.94 m@
the adsorption density of xanthate remains relatively unchanged, which suggests that the
difision of xanthate through the existing layer to react with the cupnc ion at the natural
enargite surface becomes the rate controbg factor. Fmdy, as the concentration of
xanthate increased fiirther, the adsorption density increases again.
Pure enargite did not contain iron whereas the natural sarnple contained about 9
percent of this element, which forms a p*te

type inclusion. The hydrophobic species for

pyrite is dixanthogen (Fuerstenau et ai. 1968), therefore, the formation of cuprous

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 conctusions drawn are as foiiows:

- 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 .

- Xanthate adsorption on naturai emgite can be explaineci in terrns of an ion exchange


mechanism. The hydrophobie entities responsible for flotation of nanual enargite are both
cuprous xanthate and dixanthogen.

- The floatability of natural enargite is virtudy constant at pH 6 to 9. For pH ranges


hi$er than 9 a stronger depression effect occurs.

- 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)

Figure 6.1. la: Adsorption of PAX on chalcopyrite as a function of time at pH 9

The adsorption isotherm of xanthate on the surface of chalcopyrite at pH 9 is

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

Esuilibrium Xanthate Concentration ( m d l

Figure 6.1. 1b: Adsorption isotherm for P A X on chalcopyrite.

1O00

6.1.1.1

Effect of Sodium Cyanide on Adsorption

The effect of sodium cyanide on the pre-adsorbed xanthate on chalcopyrite at 20 mg4


xanthate concentration is shown in Figure 6.1.1.1 . As the cyanide contact time increases, a
rapid desorption of xanthate from the chalcopyrite surface ocnirs. At 20 mgIl sodium
cyanide concentration, a maximum of 36 percent xanthate is removed within 120 seconds

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

Effect of Sodium Sulphide on Adsorption

The effect of sodium sulphide on the pre-adsorbed xanthate on chalcopyrite is


presented in Figure 6.1.1.2. The results show that there is a desorption of xanthate From
the sudace of chalcopyrite. Mer 5 minutes of conditioning of chalcopyrite in 10 mg/l

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
.
.
.
.
.
.
.
.

S o d i u m S u I p h i d e Contact Tim e (m inutcs)

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.

The effea of sodium sulphide on the adsorption density by pre-conditioning the


chalcopyrite sample with Na2S followed by xanthate addition is given in Table 6.1. The
results show that the adsorption density at 20 mgll xanthate concentration is about 37.4
percent of the original adsorption density.
A cornparison of the results shows that sodium sulphide exerts a higher depression

effea on the pre-adsorbed xanthate on the chalcopyrite surface than the reverse reagent
addition sequence.

6.1.1.3 Effect of KMnO4 on Adsorption

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

concentrations of 25 and 50 mgIl, respectively.

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.

The effect of KMnOd on xanthate adsorption by pre-conditioning the chalcopyrite


sarnple with KMn04 followed by xanthate addition is given in Table 6.1. The adsorption

density at 20 mg/l xanthate concentration is about 70 percent of the original adsorption


density which shows aimoa the same effect as its effect on the pre-adsorbed xanthate on
the chalcopyrite surface.

6.1.1.4

Effect of pH on Adsorption

T h e pH was varied kom 6 to 12 with sodium hydroxide at two different xanthate


concentrations as shown in Figure 6.1.1.4. The results show that the adsorption density of
xanthate on chalcopyrite decreases by increasing the solution pH. A sharp decrease occurs
at pH values higher than 9. The extent of decrease is more for the 50 mg/l PAX solution

than for the 20 mgA PAX solution.

.......

-0-

P A X C o n c . = 2 0 mg11

...&..........

...........

Figure 6.1.1.1:The fies of pH on adsorption density of PAX on chalcopwte.

6.1.1.5

Effect of Aeration on Adsorption

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

adsorption density after 20 minutes aeration.

6.1.2

Flotation

The reiationship between coiiector concentration and flotation of chalcopyrite at pH 9


is shown in Figure 6.1.2. This relaonship is a paraboiic with a sharp increase at low

concentrations and a gradua1 asymptotic approach at higher values of xanthate


concentrations. The fiotation recovery Uicreased to 90 percent at 50 mg/l and to a

maximum recovery of about 93 percent at a concentration of 100 rngl.

.......

4...

.......................................... .........................................
I

20

40

60

80

100

Original xanthate Concentration ( m g r i )

Figure 6.1.2: Fioatabiiity of ctialcopyrite.

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

Effect of Sodium Cyanide on Flotation

The effect of sodium cyanide concentration on the flotation recovery of chaicopyrite


is presented in Figure 6.1.2.1. This figure shows that the flotation recovery decreases

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

Sodium C y a n i d e Contact T i m e ( minutcs)

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).

Table 6.2: The e


e
c
t of depressants on the chalCopyrite fioarabiiity.
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

Effect of Sodium Sulphide on Flotation

The effect of sodium sulphide concentration on the flotation recovery of chalcopynte

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.

The effect of sodium suiphide on the chalcopyrite dotation by pre-conditioning with

Na2S foliowed by xanthate addition and flotation is s h o w in Table 6.2. The flotation

recovery is 26.15 percent at 10 mgA sodium suiphide concentration.

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

with 20 mg/l PAX solution. The floatability of chalcopyrite decreases strongly at pH


values higher than 10. The flotation recovery at pH 12 is about 28 percent for both P A X

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.

Figure 6.1.2.3: The d e c t of pH and PAX concentration on the floatability


of chalcopyrite.

6.1.2.4

Effect of KMn04on Rotation

Figure 6.1.2.4a. shows the effect of Kh4hOJ on the chalcopyrite flotation at 20 m u


PAX concentration. The results indicate that the chalcopyrite flotation is vimially the

same, Le., 78-81 percent with a K M ~ O concentration


J
of 0.1-10

mu. As the KMnOJ

concentrations increased above 10 mg/l, chaicopynte recovery decreased sharply. A 39


percent chalcopyrite recovery is obtained with 100 mgA KMn04.

o. 1

10

100

K M n O q Concentration (mg/])

Figure 6. I.2.4a: Floatability of chalcopyrite as a hinction of KMnOjat 20 mgA


PAX concentration.

Table 6.2 shows that 5 1 percent chalcopyrite recovery is attained by conditioning the
chalcopyrite sarnple in 50 mg/i

followed by conditioning with 20 mg/i PAX and

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

100 mg/l KMnO4 concentration. The flotation

recovery does not change fkom pH 6 to pH 9, but there is a decrease in recovery at higher
pH values.

Figure 6.1.2.4b: The e k t of pH and K M n O 4 concentration on the fioatability


of chaicopyrite at 20 mg/i PAX concentration

6.1.2.5 Effect of Aeration on Ftotation

The floatability of chalcopyrite is affected by aeration as show in Figure 6.1.2.5. The


results show that the flotation recovery decreases to about 51 percent at one hour
aeration. A smdl decrease to 46 percent in the flotation recovery of chalcopyrite is
obtained by 2 hours aeration.

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 )

Figure 6.1.2.5: The @en of aeraion conditioning on the floatabiliiy chicoppite


at 20 mg/f PAX concentration.

6.1.2.6

Effect o f Pulp Potentials on Notation

Flotation recovery of chalcopyrite was determined as a fundion of the pulp potentials


which were controlled by the addition of sodium sulphide and potassium permanganate as

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.

6.1.3 Adsorption-Fiotation Relationship

The chalcopyrite adsorption-notation relationship is presented in Figure 6.1.3. The

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

mg/m2adsorption density. As can be seen a 56 percent increase in adsorption density fiom


7.088 mg/m2 results in only a 3 percent increase in flotation recovery.

A d s o r p t i o n D c n s i t y (rn g l m ')

Figure 6.1-3: Adsorption-notation relationship for chalcopyrite.

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-

type semiconductor, chalcopyrite, shows the characteristic peaks for dixanthogen.

D b t h o g e n is also found to be the major species on chalcopyrite by AUison et ai. (1972).


The solubilization of copper or uon fiom the mineral aiso plays an important role. As
shown by Ackerman et ai. (1987), the solubiiity of copper fiom chalcopyrite is substantial.
These solubilized ions cm cause the rapid oxidation of xanthate to dixanthogen.
Therefore, it is concluded that the hydrophobie species responsible for flotation of
chalcopyrhe are both cuprous xanthate and dixanthogen.

6.2.2

Flotation

The effect of colleaor concentration at pH 9 on the flotation of chalcopyrite using

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

The effect of sodium cyanide on the pre-adsorbed xanthate on the chaicopyrire


surface is s h o w in Figure 6.1.1.1. Initidiy xanthate is removed fiom the chalcopyrite
surface by cyanide. This initial desorption is followed by an inaease in the adsorption
density after 2 minutes conditioning. The presence of fke cyanide ions causes the
dissolution of cuprous xanthate and desorption of xanthate fkom the chaicopyrite sdace.
The interaction of cyanide with the metai surface after solvation of the collecter film
causes the formation of copper cyanide complexes which reduces the copper sites and thus
funher formation of cuprous xanthate. Dixanthogen, on the other hand, is decomposed to

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):

(ROCSS)2+ 2CW + Z(R0CSS)' + (CN')2


(ROCSS)2+ C N

+ (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.

The depression of chalcopyrite is unstable. It appears that an increase in contact time


which reduces the depression effect of cyanide is due to the depietion of cyanide in the

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

Effect of Sodium Sulphide

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

chalcopyrite notation system. The depression mechanism of sodium sulphide on


chalcopyrite is rnainly due to its reducing property. It is well known that under strongly
reducing conditions the oxidation potential of the solution will be lowered and
dixanthogen cm not be formed (Castro 1979). Additionaily, when the sulphide ion is used

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

chalcopyrite, anything that would decrease their effective concentration or rate of


formation would decrease the fioatability of this mineral.

6.2.7 Effect of Aeration


As sulphide minerals are susceptible to oxidation, there is no doubt that oxidation has

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.

63.8 Effect of Pulp Potentials

The small-amplitude cyclic voltametric (SACV) measurements demonstrated a


possible participation of dixanthogen and cuprous xanthate species on the chalcopyrite
flotation (Roos et al. 1990). However, if the potential of the chalcopyrite depended only

on the presence of dixanthogen as proposed by Mison et al. (1972) it would be expected


that its floatability would be increased at potentials higher than the equilibrium potentials

of decomposition reactions of cuprous xanthate species. Electrochemical-rnicrofiotation


tests for chalcopyrite are shown in Figure 6.1.2.6. The floatability observed at -460 m V
vs. SCE is 12.5 percent. It is clear that the onset of floatability coincides well with the

equilibrium potential of the reaction proposed by Richardson and Walker (1 985):


CuFeS2 + X

CuX + FeS2 + e- (EO = -719 mV) (6.2.8.1)

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.

The cornpiete flotation of chalcopyrite is consistent with the reaction:


2X=X+2

(EOz-159mV) (6.2.8.2)

where, at a xanthate concentration of 20 mg/l (9.9~10"M), the potential of dixanthogen


formation is -164 mV (SCE), which then corresponds to 80 percent chalcopyrite recovery

in Figure 6.1.2.6.Chalcopyrite floatability is decreased by oxidation, but the effect seems


not to be very strong below +150 rnV(SCE).

6.3 Conclusions

In order to compare the results of the adsorption, flotation and depression


characteristics of enargite and chalcopyrite, an attempt has been made to study the

characteristics of chalcopyrite under the same conditions. From the results obtained, the
following conclusions can be aated:

- Xanthate adsorption on chalcopyrite can be explained in terms of an ion exchange


mechanism.

- 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

recovery of 90 percent was obtained at a xanthate concentration of 50 mgA. An

increase of 2.75 percent in recovery was achieved by duplicating the xanthate


concentration.

- There

was a considerable decrease in flotation for high alkaiine media due to the

decomposition of dixanthogen.

- The flotation of chalcopyrite was potential-dependent

between -462 and +286 m V vs.

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

d e r an extended penod. After 20 minutes contact at a cyanide concentration of 15 m g ,


the xanthate adsorption density increased causing a 30.31 percent nse in flotation

recovery. The excess cyanide concentration resulted in chalcopyrite depression.

- Increase in sodium sulphide contact time increased the desorption of xanthate from the
surface of chalcopyrite.

- Potassium permanganate had the

same effect as cyanide but a higher permanganate

concentration is needed to achieve the same results..

CHAPTER 7
Cornparison of the FIotation Chemistry of Synthetic Enargite,

Natural Enargite and Chaicopyrite

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 )

Figure 7.2a: The adsorption of PAX on miner& as a function of time at pH 9


and 20 mgA PAX concentration.

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

a Langmuir type plot.


Figure 7.2b also shows that natural enargite has the highea adsorption density and
chalcopyrite has the lowea adsorption density. The adsorption density of synthetic
enargite is between that of the two other minerals for equilibrium xanthate concentrations
of Iess than 4 mg/l. When the equilibrium xanthate concentration is higher than 4

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

Equilibrium Xanthatc Concentration (m g / l )

Figure 7.2b: Adsorption isothenns for PAX on minerals at pH 9.

The order of magnitude of adsorption density of xanthate on synthetic enargite is


higher than natural enargite and chalcopyrite up to an initiai xanthate concentration of 20
mg11 but this trend is reversed for higher initial xanthate concentrations which results in

stronger adsorption density for natural enargite and chdcopyrite.

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

depressing reagent is required.

7.2.1

Effect of Sodium Cyanide on Adsorption

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.

At 15 mg/I sodium cyanide concentration, there is a desorption of xanthate from the


chalcopyrite surface at the start of the sodium cyanide addition up to 2 minutes, this

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

Sodium C yanide C o n t a c t T i m e (m inutes)

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

surfaces of minerals after 10 minutes contact is in the following order:


synthetic enargite > natural enargite > chalcopyrite.

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.

The effect of sodium cyanide on the xanthate adsorption, evduated by 10 minutes of

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

adsorption density at 20 mg/l xanthate concentration for synthetic enargite, naturd


enargite and chalcopyrite, respectively.

Table 7.2: T'he effect of depressants on the .uanthate adsorption on synthetic enargite.
natural enargite and chalcopyrite.

Test Conditions

Initial PAX Conc.=20.0

Minerai
Onginai
3.99 1
Synthetic
Enargite
Naniral
2.859
Enargite
Chal~op~yite 2.789

NaCN
15 mgi
0.894

ma. ConditioningTirne=IO min.. pH=9.0

Adsorption Density mg/m2


First Conditioned With Depressant. Then With Xanthate
%
Na$
%
%
KMn04
Aeration
10 mg/l
50 mgA
20 min.
2.716
22.40
68.05 2.275
57.00
2.395

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

xanthate fiom the enargite surface can be explained by the

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

thiocyanate as an intermediate and then decomposing

to dialkyl mono sulphide and thiocyanate as discussed in a previous chapter. It should be

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.

7.2.2 Effect of Sodium Sulphide on Adsorption

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

From the results chalcopyrite could be depressed by Na2S.

The effect of sodium sulphide on the xanthate adsorption, evaluated by conditioning


the mineral samples with Na2S followed by the xanthate addition, is given in Table 7.2.

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

differences observed for enargite and chaicopyrite.

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

Effect of KMn04 on Adsorption

Figure 7.2.3 shows the effect of permanganate on pre-adsorbed xanthate for synthetic

has the strongea

enargite, namral enargite and chalcopyrite. Results indicate that %O4

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.

The effect of permanganate on xanthate adsorption density, which was stuclied by


conditionhg the mineral sampies with KMnO4 followed by the xanthate addition, is aven
in Table 7.2. As can be seen fkom this table, permanganate has the strongest depression

effect on synthetic enargite and the least depression effect on chaicopyrite.


The reaction between permanganate and xanthate results in the formation of

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.

7.2.4 Effect of pH on Adsorption

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

pyrite may contribute to the dimuiishing adsorption density of naturd enargite at pH

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

Figure 7.2.4: The &&t of pH on the adsorption density of PAX on rninerals at


20 mg11 PAX concentration.

7.2.5

Effect of Aeration on Adsorption

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,

respectively. As these rninerals are susceptible to oxidation, the formation of cupnc or

arsenic oxides on the surface depresses their notation.

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 )

Figure 7.3 : Fioatabiiity of synthetic enargite. nacurai enargite and chalcopyrite at pH 9.

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@

PAX concentration. Above 20 mg/i xanthate

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:

chalcopyrite > synthec enargite > natural enargite.

Thus, it is concluded that more than 10 m@

xanthate is required to obtain higher

recoveries and a higher concentration of xanthate is preferred for chalcopyrite. The


concentration of xanthate is therefore recommended as 30 mg/'for the separation tests.
The results of flotation tests aiso show the shilarity of the flotation characteristics of

synthetic enargite, nahiral enargite and chalcopyrite.

7.3.1 Effect of Sodium Cyanide on Flotation

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,

naniral enargite and chalcopyrite, respectively (Table 7.4).

Table 7.1: The &ect of depressants on the synthetic enargite. naturai enargite
and chaicopyrite floaability.

Test Conditions

Initial PAX Conc.=20.0

ma,Conditioning Time=10 min.,

pH=9.0

F i Conditioxng With Depressani Then ~ l o t a ~ -o n


Mineral

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

7.3.2 Effect of Sodium Sulphide on Rotation

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.

Sodium Sulphide Contact T i m e (minutes)

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).

7.3.3 Effect of pH on Notation

The effect of solution pH on the floatability of the three minerals is s h o w in Figure


7.3.3. In general, the flotation recovery was virtually constant between pH 6 and 9.

The order of mineral flotation is typicaily as follows:


chalcopyrite > synthetic enargite > natural enargite.

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.

7.3.4 Effect of KMn04 on Notation

The effect of permanganate concentration on the floatability of the three minerals is


presented in Figure 7.3.4. An increase in permanganate concentration depresses synthetic
enargite, and at 100 mg/l KMnOI concentration the recovery decreases to about 22
percent. At this concentration the floatability of natural enargite is about 30 percent. The
chalcopyrite floatability decreases with increasing permanganate concentration and is
about 39 percent at 100 m g KMn04 concentration. At less than 10 mgll KMnOJ
concentration, permanganate somewhat reduces the floatability of synthetic enargite, while
naturai enargite remains almost unaffected due to its pyrite impurity. Oxidation has less

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 )

Figure 7.3.5: Fioatability of minerais as a function of KMnOj concentration at pH 9


and 20 mg/t PAX concentration.

After 10 minutes conditioning of the minera1 samples in 50 mgA M O 4


concentration, the flotation recoveries were 45.08,47.35 and 50.91 percent for synthetic

enargite. naturai enargite and chalcopyrite, respectiveiy (Table 7.4).

7.3.5 Effect of Aeration on Notation

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

synthetic and natural enargite to 30 and 32 percent, respectively. The floatability of

chalcopyrite decreases to about 46 percent after 2 hours aeration. The oxidizabiiity of


minerals is in the following order:
synthetic enargite > naturai enargite > ctralcopyrite.

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

that of chalcopyrite. A significant merence between notation recovery is not observed


even at prolonged aeration conditioning. Aiso extended aeration time causes the

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. .

7.3.6 Effect of Pulp Potentials on Flotation

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-

1 O 0 200 300 400


SC E)

7.3.6: Relationship between flotation recwery and pulp potentiaf for minerals
at pH 9 and 20 mg/l PAX concentration.

7.4 Laboratory Scale Flotation

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

the Hallimond tube tests.

Table 7.5 : Labontory scale fotation of synthetic enargite. nanuai enagite


anci chahpyrite.
Test Conditions
Sia. g
Mineral, g
pH

Conditioning Time. min.

Fmther(Aerofioth 65). drops


Flotation Tirne. min,
P

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 adsorption, notation and depression characteristics of synthetic enargite, natural


enargite and chaicopyrite were compared. The conclusions drawn are as follows:

- 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.

- The results of the micro-dotation technique were confimed

with the results of the

Denver laboratory flotation cell.

- The floatability of the three minerals is virtuaily the same at pH 6 to 9. At pH regions


higher than 9 a stronger depression effect occurs on chalcopyrite.

- 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.

Sodium cyanide and potassium permanganate have a stronger depression effect on

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.

By conditioning the minerai surface with a depressant foilowed by flotation it was

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

partially separated from chalcopyrite by cyanide for extended contact times.

- 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 sulphide minerais ocnir occasionaily with arsenic minerais, particuiarly


enargite (Cu3AsSa) and ternantite ((CuFe)l&&).

In sulphide mineral flotation, a

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

arsenic from the concentrates. In pyrometailurgical methods conventional roasting of


copper concentrates or alternatives to this method (Le., nonoxidative techniques such as
electric nimaces, rotary kilns) for arsenic removai are used. The roasting and smelting of
arsenical concentrates have aiways involved problems in handling the arsenic compounds
(Kusik and Nadkami 1988). Arsenic is nomaily produced in a roasting operation in the

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

enargite is close to the specific gravity of chalcopyrite, gravity concentration is not


applicable. However, the froth flotation technique seems to be a suitable rnethod of
reducing the arsenic content of copper concentrates.
The investigations discussed in the previous chapters have identified the conditions in
which each mineral can be floated with PAX. It would appear that this information could
lead to the developrnent of strategies for selective flotation. This work, which focused on
a detailed physicochemicai characterizaion of the surface composition of these three
minerals in relation to flotation, provides a basis for the separation of these rninerals under
controlled conditions.

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.

If an extrernely hi@ selectivity is wanted (Le., no As in the concentrate) the theoretical Cu


recovery cannot exceed 67.3% for this sample.

8.2.2

Resuits

The variabies investigated in the laboratory study of enargWchalcopyrite flotation


separation are sumrnarized in Table 8.1. With an increase in the collecter concentration
from 10 mg/l to 30 mgfl there was an increase in the copperhrsenic separation efficiency
(defined as the copper recovery minus the arsenic recovery (Schulz 1970)), from 3.47
percent to 7.32 percent. As recommended in the previous chapters and based on the above
rnentioned results the concentration of xanthate was therefore selected as 30 mgIl for the
other tests. The type of pH modifier was tested at various pH vdues. When NaOH was
used the copper/arsenic separation efficiency was maximum at pH 9. The separation
efficiency was higher using lime at the sarne pH. Using lime as a pH modifier resulted in
bener rejection of arsenic, however, the arsenic recovery was still very high and the
percentage of arsenic in the concentrate was 4.3 1. The eEect of NaCN was tested for 5
and 20 minutes conditioning with NaCN at 15 rngA concentration. Mer 5 minutes NaCN

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

maximum copper/anenic separation effitiency of 17.39 percent with an arsenic recovery


of 48.54 percent for 10 minutes contact at 25 mg/i K A 4 1 0 4 concentration. Aeration
conditioning, on the other hand increased the copper/arsenic separation efficiency dong
with decreashg the arsenic recovery and a decrease in the copper recovery. This is

because aeration preferentidy depresses enargite and therefore there is an improvement in


the separation efficiency.

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

contact times of 5 and 20 minutes, respectively. Therefore the maximum separation

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

of notation conditions for separating enargite and chaicopyrite. The irnplernentation of


lime as a pH modifier at a PAX concentration of 30 mg/I and pH 9 dong with use of an
appropriate amount of sodium cyanide as a depressant represents a good arsenic rejection.
As can be seen from the results a 24.24 percent copper/arsenic separation efficiency or an

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

of 26.89 percent copper/arsenic separation efficiency, corresponding to 2.1 8 percent


arsenic, was attained.
Note, fiom Table 8.1, that the flotation results of dEerent flotation conditions are
similar. For example there are very similar copper/arsenic separation efficiencies by either
30 minutes aeration or 10 minutes contact with 25 m g

KMn04.The arsenic grades are

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

Cu is extracted by direct leaching. Such a hydrometallurgical extraction may be

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:

- Separation efficiency was a maximm when using 20 mg/i NaCN as a depressant at a


contact time of 20 minutes. A separation efficiency of about 24.15 percent was obtained
with the use of Na2S as a chalcopyrite depressor. The same results were also obtained
when 15 mg/l NaCN was used at the same conditions.

- .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.

Selective Depression of Enargite by a Mapesium-Ammonium Mixture

9.1 Introduction
The renilts obtained in the previous chapters demonstrated that the selective flotation

of enargite and chdcopyrite was characterized by a low separation efficiency using


conventional depressants. To overcome this problem the application of a new and
selective depressant for enargite was investigated.

The application of a mixture of magnesium chioride (MgC12.6H20), ammonium


chlonde W C l ) and ammonium hydroxide W O H ) ,

MA4 as a depressant for enargite

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.

9.2 Experimental Techniques

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

measured and used to calculate the surface tension.

9.3 Results
9.3.1 Adsorption

A preliminary study of the xanthate adsorption density on synthetic enargite. natural

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

densities for synthetic and natural enargite, respecfvely. No meamrable decrease in


adsorption density was observed for chalcopyrite at any MAA concentration.

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

Adsorption Density. mg/m2

Conditioning
Tirne
(min.)

0.0
5.0
10.0
20.0

PAX Conc., 20 mgil


Synthetic
Nanuai
Enargite
Enargite
2.859
3.991
1.885
1.493
0.488
0.702
0.686
0.480

PAX Conc.. 30 mgh


Synthetic
Natural
Enargite

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. la: The &ect of MAA concentration on adsorption dewity of . a l h a t e on


minerals at pH 9 and 20 mg4 PAX

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 .

Figure 9.3.1b: The &ect of pH on the adsorption density of PAX on minerals


at 20 mgIl PAX concentration and 250 mg/l MAA.

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

adsorption density on chaicopyrite in the pH range of 7 to 1 1 shifts from 2.994 mg/mz to


2.175 mg/m2.
A series of tests was performed using 10 minutes aeration (air oxidation) of synthetic

and naturai enargite before conditionhg with MAA at pH 9. The results presented in

Table 9.1 show a hrther decrease in adsorption density.

The effect of 250 mgA MAA on

synthetic and natural enargite which had been pre-

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 9.3.2a: The e t k t of MAA concentration on the foatabiiiryof minerais at


pH 9 and 20 mg/l PAX concentration.

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

>

-C- Synthctic Eaargitc

- ............................ ..................-....... +Natural Enargite

8 0 -...........
7 0 - ...............5 ...............

...............

Figure 9.3.2b: The efkct of pH on fioatability of minerais at 20 mgA PAX


concentration and 250 mg/l MAA.

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

decrease in chaicopyrite recovery.


With an increase in PAX concentration fiom 20 mg/l to 30 mg/'at pH 9, there was an

increase in flotation recovery of synthetic enargite, nanird enargite and chalcopyrite to


1 1.28, 16-07 and 85.55 percent, respectively (Table 9.2). At a PAX concentration of 20

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.

Table 9.2: The &ect of MAA on the fioatability of ~yntheticenargite,


nanuai enargite and chalcowte.

Test Conditions
MAA Concentration = 250.0 mg/L Conditioning T e = 10 Min.. pH = 9.0

%R

P A X Concentration = 20.0 rn@


Synthetic Enargite
Naturaf Ewgite

9.24
14.53

Aeration = 10 min. Then Conditioning With MAA


PAX Concentration = 20.0 mg/l
6.90
Synthetic Enargite
Naturai Enargite
12.2 1
Chalcopyrite
79.20
PAX Concemation = 30.0 mg(l
Svnthetic Enargite
1
11-28
Natural Enargite
16.07
Chalcouvrite
85-55
-

9.3.3 Surface Tension Studies

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.

The feasibility of enargite-chalcopyrite separation in the flotation of a copper ore, at


reduced surface tensions regulated by methanol, was investigated. It was found that by
varying the methanol dosages From O to 50 percent v h , no selectivity could be obtained

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

process is based on the different wettabily behaviour exhibited by enargite and


chaicopynte using MAA.
Figure 9.3.3b illustrates the effect of surface tension on the floatability of enargite and

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.

Seleetive Depression of Enargite

9.3.4

A feasibility snidy on the selective sepamion of chalcopyrite and enargite was

conducted on a mixture of minerais. An adficiai mixture of 0.5 grams synthetic enargite


and 5 gram chalcopyrite was used for the notation tests in a modi5ed Hallimond tube.
This artincial mixture and aqueous solution of MAA were introduced into the cell. The
pulp was conditioned for 10 minutes, after which xanthate solution was added into the ceil
and then conditioned for 20 minutes. The flotation time was one minute. The standard

conditions were 30 m

g PAX, 250 m g MAA and pH 9. The variables were aeration time

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

Under the standard conditions (without aeration and methanol), a separation

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

anions of anenate with covalent bonding [ASO~]".According to the Eh-pH diagrams


showing arsenic compounds, arsenate is stable over a fairly wide pH range (Mina et al.
1988). Oxidation of MO)or A s 0 to As(V) puts it among the cations with high ionic

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

compound As04N&Mg.6Hz0. This inhibits the adsorption of xanthate on the surface of


enargite leading to its depression whde xanthate is adsorbed selectively on the chalcopyrite

surface. This is supported by the faa that arsenic is quantitatively detennined by


precipitation fiom ammoniacal solution with a magnesia mixture such as magnesium

ammonium arsenate, AsOiN&Mg.6&0

(Remy,1956). As is seen fiom its composition.

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.

Figure 9.4: Infrared spectra of d a c e compounds formed on the synthetic enargite


nirface aAer matment with m.

9.5 Conclusions

The following conclusions have been reached:

A new and effective depressant for enargite was developed using a mixture of

magnesium chloride, ammonium chloride and ammonium hydroxide

m).

The adsorption density of xanthate on synthetic and natural enargite decreased

significantly by using MAA while no measurable decrease in adsorption density was


observed for chalcopyrite.

- 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.

- Enargite and chalcopyrite showed a merence in floatability in a medium of reduced


surface tension. The combination of reduced sdace tension and MAA enhanced the
separation efficiency of enargite and chdcopyrite.

- 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.

The control of surface tension by adjusting the flotation medium appeared to be

successful in the selective flotation of chalcopyrite nom enargite. A reduction of arsenic

from 1.73 to 0.14 percent was attained by using a 2 percent (vh) solution of methanol.

- Conditioning with

a combination of aeration and MA4 and 2 percent rnethanol

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

10.1 Summary and Conclusions

In this investigation the adsorption, flotation and depression characteristics of enargite


and chalcopyrite were extensively snidied. An understanding of the d a c e propenies of
these minerals as well as the pulp chemists, rnight lead to improve enargite flotation
performance. A detailed cornparison between the characteristics of enargite and
chalcopyrite surfaces might be employed for the selective flotation of these minerais using
xanthate collectors and suitable depressants.

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.

This is friendly to the environment.

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:

Conclusions from the study on synthetic enargite:

Xanthate had a very high afFNty for synthetic enargite. The adsorption density was

reasonably high. The adsorption process is a chemisorption.

- The hydrophobie species responsible for synthetic enargite flotation

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

obtained at a xanthate concentration of 50 miJi in the pH range of 7-9.

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.

Conclusions fiom the study on natural enargite:

The results of adsorption and flotation studies indicated that a maximum recovery of

83 .O percent was obtained at a xanthate concentration of 50 mg/l which corresponds to an

adsorption density of 7.484 mg/m2.

The floatability of natural enargite was vimially constant at pH 6 to 9. At pHs higher

than 9 a stronger depression effect was observed.

Sodium cyanide and potassium permanganate had a stronger depression effect than

sodium sulphide on natural enargite.

It was s h o w that Eh has a controlling influence on the notation of natural enargite.

Conclusions fiom the study on chalcopyrite:

- 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

to the decomposition of dixanthogen.

- 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

sarne effect as cyanide but at a higher permanganate concentration. The effects of


depressants on chdcopyrite were in the following order:
sodium sulphide > potassium permanganate > sodium cyanide

Conclusions from the cornparison study of enargite and chalcopyrite:

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

an oppominity for separating these mixtures by differential flotation.

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.

Conclusions fkom the selective separation study of enargite and chalcopyrite:

By using sodium cyanide, potassium permanganate and aeration the reduction in the

arsenic grades were 54, 23 and 27 percent, respeaively.

Using sodium sulphide as the chaicopyrite depressor resulted a 3 1 percent reduction in

the arsenic grade.

A new and effective method for depressing enargite was developed by the application

of a mixture of magnesium chloride, ammonium chlonde and ammonium hydroxide


(MAA).

Implementation of 250 mg/l MAA as the enargite depressor at a collecter concentration

of 30 mg/l PAX and pH 9 dong with pre-aeration resulted in a 90 percent reduction in


arsenic grade.

The control of surface tension by adjusting the flotation medium with methanol

resulred in 92 percent reduction in arsenic grade.

10.2 Recommendations for Future Study

Several recommendations for fiiture research in t h fieid can be made. These include:

To gain a better understanding of enargite dissolution chemistry. surface oxidation

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

rnechanisrns and reaction products.

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.

To separate a chalcopyrite-enargite rnixnire by extemal potential control, pulp

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.

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72. 1963, pp. 715-72 1.
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Appendix A l

X-ray Diffraction Anaiysis of Synthetic Enargite

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

characteristic of the target metal, a sharp intensity maximum appears at cenain


wavelengths. which supenmposed on the continuous spectmm. These so-called
"characteristic lines" fall into severai sets, referred to as K, L, M, etc., in the order of
increasing wavelength. Al1 the lines together fom the characteristic spectmm of the metal
as the target.
The origin of the characteristic spectmm lies in the atoms of the target material itself

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

f o m of radiation of a definite wavelength and is, in fact, characteristic K radiation.


Ordinarily only the K lines are usehl in x-ray difiaction, the longer-wavelength lines
being too easily absorbed.

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

of the radiation used (x-ray spectroscopy).

Bragg's law is written as: X = 2d Sine

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.

Figure A 1. X-ray dilnacuon pattern of syntheuc margite.

Appendix A2

Calculation of Adsorption Density


Bushell and Mainarich (1956) developed a simple quantitative spectrophotometric
method for the analysis of xanthate in aqueous solutions based on the ability of the
xanthate rnolecule to adsorb light. The aqueous xanthate solutions are analyzed directiy on
a spectrophotometer with no pnor cornplexkg, or chernical treatment, being required.

They obtained the spectmm of a solution of puriied xanthate in a Backman DU


Spectrophotorneter, and the peak at a wavelength of 3010 d provided a suitable buis for
the analysis.

The results of xanthate adsorption tests presented in Appendix A9 were determined


using the procedure descnbed in section 3.2.1.The solution concentrations of amyl
xanthate were determined with a Perkin-Elmer lambda 3B WMS Spectrophotometer. In

those cases, where the xanthate concentration exceeded 20 m g . a measured volume of


the solution was accurately diluted.

Appendis A3

Surface Area Determinations


The surface area of the sample was determined ushg the Brunauer, Emmen and
Teller (BET) (1938) method of gaseous adsorption. They proposed a theory for
multimolecular adsorption systems. in essence they denved the following equation to
describe gaseous multimoiecular adsorption isotherms:
P/[V(P,-P)] = 1/p,C] + [(C- 1)P]I[V,CP.]
where
P. = liquefaction or saturation pressure

P = pressure of adsorbing gas


V, = volume required for complete monolayer coverage

V = volume adsorbed

C = a term related to the heat of adsorption

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

Cross sectional a m of PAX per xanthate radical (ionic radii) = 25A2 = 25

10-I6 cm2

It is assumed that each xanthate group covers an area of 25A2

MoIecuIar weight of PAX = 202 g

Number of molecules in 1 gram molecular weight (Avogadro's Nurnber) = 6.023

10"

Specific surface area of synthetic enargite = 0.4991 m21g = 4991 crn2/g

- Number of moles of PAX to cover 1 gram synthetic enargite = 4991/(25


x 10") = 3.32 x lod mol PAX/gram of synthetic enargite

x 10''~x 6.023

Monolayer for 1 gram synthetic enargite at 0.4991 m21grequires:


3.32 x

'OI

x202000=0.671 mg/g

- Nurnber of moles of PAX to cover 1 gram natural enargite = 7225/(25


I oz) = 4.80

x 10"~x6.023x

1o4 mol PAX/grarn of naturd enargite

Monolayer for 1 gram naturai enargite at 0.7225 m2jg requires:


4.80 x 104 x202000= 0.970 mg/g

- Number of moles of PAX to cover 1 gram chaicopyrite = 6496/(25 x


= 4.3 1 x 1
0
'

mol PAX/grarn of chalcopyrite

Monolayer for 1 gram naturd enargite at 0.6496 m2/grequires:


4.31 r

lod x202000= 0.871 mg/g

10-'~x6.023
w 1 on)

Appendk A5

Cdculation of the Recovery


The method of calculation of the recovery is as follows:
1-5 g of chalcopyrite contains = 0.0 15 x 33.2 = 0.498 g Cu

1.5 g of chalcopyrite contains = 0.015 x 29.9 = 0.449 g Fe


0.5g of enargite contains = 0.005 x 48.4 = 0.242 g Cu

0.5 g of enargite contains = 0.005 x 19.02 = 0.095 g As

The percentage of Fe and As in the artificial mixture is:


% Fe = 0.449/2 x 100 = 22.45
% & = 0.095/2x 100 = 4.75

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

Thus the percentage of total copper in the ariificiai mixture is:


% Cu = 12.1 + 24.9 = 37.0

The Cu/As ratio in the artificial sample (2 g) is 7.79.

- Recovery of chdcopyrite = 100

percentage of Fe in the concentrate

weight of

concentratd0.449

- Recovery of enargite

= 100 x percentage

of As in the concentrate

weight of the

concentrate10.095

%Cu contnbuted by chalcopyrite in the concentrate = recovery of chalcopyrite

0.498Iweight of concentrate

- %Cu contributed by enargite in the concentrate = recovery enargite x 0.24Uweight of


concentrate

- Recovery of Cu = % Cut x weight concentrate/0.740


- Recovery of As = %As x weight concentrate/0.095

5 g of chalcopyrite contains = 0.05 x 33.2 = 1.660 g Cu


5 g of chalcopyrite contains = 0.05

29.9 = 1.495 g Fe

0.5g of enargite contains = 0.005 x 48.4 = 0.242g Cu


0.5 g of enargite contains = 0.005 x 19.02 = 0.095 g As

The percentage of Fe and As in the artificial mixture is:


% Fe = I.495/5.5 x 100 = 27.18
% As = 0.095/5.5 x 100 = 1.73

The percentage of Cu contributed by enargite in the amficiai mixture is: 0.24U5.5

100 =

4.4

The percentage of Cu contributed by chalcopyrite in the artificial mixture is: 1.66/5.5x


100 = 30.18
Thus the percentage of total copper in the artificial mixture is:
% Cu = 30.18 + 4.4= 34.58

The Cu/& ratio in the artificial sample (5-5 g) is 19.99.


- Recovery of chalcopyrite

= 100 x percentage

of Fe in the concentrate

weight of

concentrate/ 1.495

Recovery of enargite = 100

percentage of As in the concentrate

weight of the

concentrate/0.095

%Cu contributed by chalcopyrite in the concentrate = recovery of chalcopyrite

I .Wweight of concentrate

- %Cu

contributed by enargite in the concentrate = recovery enargite x 0.242height of

concentrate

- Recovery of Cu = % Cut x weight concentratdl .902


- Recovery of As = %As x weight concentratd0.095

Appendix A6

Purification of Potassium Amy1 Xanthate

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.

2- Filter the solution.

3- Add 2 Iirten of petroleum ether to the filtrate to precipitate xanthate.


4- Filter out the precipitate and redissolve in 500 ml o f acetone.

5- Refilter the solution.


6- Slowly add 2 litres of petroleum ether to the fdtrate to precipitate the punfied

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

quantity of activated carbon.


1 1- Replace the acid daily until no further evaporation of ether is evident.

Appendix A7

Method of Chernical Andysis


The chesnical analyses for copper, arsenic and iron were deterrnined using a PerkinElmer mode1 23 80 Atomic Absorption Spectrophotometer. The basic principles of atornic
adsorption can be surnmarized as follows:
The production of atoms fiom molecules requires the absorption of energy, usually it
is supplied in the fom of heat. A compound when vaporized by heating in a Barne, is
partially or whoily dissociated into its elements in the gaseous fom. Some of these atorns
are further excited to a state f o m which they cm emit radiation on retuming to the
unexcited state. The relation between the number of atoms Nj, in an excited aate and the
number, No, remaining in the ground state, is given by:
Nj/No= PJP, exp(-EJ)/(KT)

where

P, and P, are the statistical weight of the two nates


EJ is the energy difference

K is the Boltzman constant


T is the absolute temperature
The higher the value of EJ (Le., the shoner the wavelength of the spectral line
corresponding to the transmission between the ground and excited state) the smaller will
be the fiaction of atoms in the excited state.
At the temperatures attainable with conventionai flames, only a small fraction of the
atoms of even the most easily excited elements such as zinc, only an insignificant fiaction
of the atorns are excited. If the absorption of light by the atoms in the highly populated
ground state is measured, the same order of sensitivity can be expected for zinc as for
cesium.
Atoms in the ground state c m only absorb radiation at a Iimited number of

wavelengths, corresponding to their resonance lines. In atornic adsorption spectroscopy


the first resonance line is most cornmonly used, being usually the most sensitive. In some

cases less sensitive resonance Iines may be used if it is desired to extend the andyticd

range to major constituents.

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.

However. if a source ernitting a strong sharp line of the appropriate wavelength is


available, then radiation hom this source cm be directed through the atomic vapour and
into the monochromator, which now needs only separate the desired line from any others
emitted by the source. If the width of the ernission line fkom the source is negligible
compared with that of the adsorption line in the atomic vapour, then the absorption
coefficient at the peak of the line is proportional to the concentration of atoms in the
vapour.
Each of the samples was accurately weighed and dissolved in concentrated n h i c acid,
boiling continuously for about 15 minutes. After filtering and washing into 100 ml
volumetric flasks. each sample was diluted to the mark with distilled water. If required
further dilution was made to bring the unknown sample into the range used on the unit.

Appendix A8
Method of Sulphur Anaiysis

The SC-444DR Carbon and Dual Range Sulphur Analyzer is a non-dispersive,


infiared, digitally controlled instrument designed to meanire the carbon and sulphur
content in a wide variety of materiais.

AU molecules, with the exception of dipolar species nich as N2, H2,and OZ,absorb in
the infiared region. Because no ~o

compounds absorb the sarne way, infrared

spectrometry is an extremely usefid method for qualitawe and quantitative chernical


analysis. As radiant energy is projected through the sample material, an infrared absorption

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

a second calcium fiuonde window, a precise wavelength filter selectively blocks dl


wavelengths. except that of CO2 and SO* fiom passing into their respective condensing

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

Initial .uanthate concentration = 15.0 mg/l = 0.795 mg


Aiiquot 1 Chan Value 1 mg in 1
mg
Adsorption Density
1 (mgil) 1 Solution 1 Adsorbeci 1

Test ( Adsorption
No. 1 Tirne (min.)

Tesi

1
2
3
4

1
1

Adsorption

5-0

[ No. ] Time (min.) 1

5
6

Test
No.

10.0
15.0
30.0
60.0
120.0

Adsorption
Tirne (min.)

1
*

ma

Initial .uthate concentration = 20.0


= 1.060 mg
Aliquot 1 Chan Value 1 mg in 1
mg
1 Adsorption Density
1 (rnfl) 1 Solution 1 Adsorbed 1
mgmmgig
1.497
2.999
Straight 1
5.88
1 0.312 1 O.748
1.770
0.175
0.885
3 S-57
3.3 1
1.824
O. 148
0.912
3.655
2.80
0.946
1.892
2.15
O.114
3.791
0.996
1.992
1-22
3.99 1
0.064
2.056
0.032
1 .O28
4.120
0.6 l
Initial . u t h a t e concentration = 50.0 me/l= 2.650 mg
Adsorption
Miquot Chan Value
mg in
Conc.
mg
Density
Solution Adsorbed
(mgm

&
.

.
&

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

The Effect Of NaCN On Adsorption Density Of PAX On Synthetic Eoa*te


Test Conditions
NaCN Concentration = 15.0 mg& Conditioning Tirne= 10 min.
SampIe weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bottle voIume = 53.0 ml. Agitated at 30 r.p.m. and Cenuifueed for 30 seconds
Initiai Conditions
Test
Xantha te
Aiiquot
Chan Value Concentration
mg in Solution
No. Concentration
(mg)
(mgfi)

(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

Table 4.1.f .2b


The Effect Of Sodium Sulphide On Adsorption Density Of PAX O n Synthetic Enargite
Test Conditions
NazS Concentration = 10.0mg/l. Conditioning Time=IO min.
Sample weight = 0.5000g, Solution pH = 9.0(Adjwted with NaOH). Adsorption time = 60 min.
Bottie volume = 53.0mi. Agitated at 30 r.p.m. and Centnfged for 30 seconds
Initial Conditions
Test
%xtth~te
Aiiquot
Chart Vake Concentration
mg in SoIution
No. Concentration
(mg)

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

C S 0 4 Concentration= 25.0 mgil


0.1 1
0.005
0.0 13
0.24
0.36
0.0 19
0.936
17.65
47-52
2.5 18
CuS04 Concentration = 10.0 mg/l
0.4 1
0.022
0.45
0.024
1.17
0.062
25.94
1.375
66.13
3 .505

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.

Equilibrium Adsorption Of PAX On Synthetic Enargite


Test Conditions
Sampie weight = 0.5000g, pH Adjusted with NaOK Adsorption cime = 60 min
Bottle volume = 53.O m i Agitated at 30 r.p.rn and Cenufuged for 30 seconds
Initiai Conditions
Xanthate
mg in Soluuon
Chart Value Concentration
Aiiquot
Concentration
(mgn)

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

The Effect Of CuSO4 Concentration On The Floatability Of Synthetic Enargite


PAX Concentration = 20.0 mfl.pH = 9.0
Test No.
Cu" Concentration (mgil)
% notation Recovev
I

74.95

0.0

TabIe 41.2.6
. The EffectOf Aeration Conditioning On The FloatabiIity Of Synthetic Enargite

PAX Concentration = 20.0 mg/l. pH = 9.0


Test No.
1

Aeration Time (min.)


0.0

% Rotation Recovery
74.95

Table 4.1. Ja

The Effect Of pH On Contact Angle Of S ~ t h e t i cEnargite


Test

Contact Angle ( Degree)

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.

Sample weight = 0.5000 g, Solution pH = 9.0 [Adjusted with NaOH)


Bottie volume = 53.0. Aejtated at 30 r.p.m. and Centrifugeci for 30 seconds
Initiai mthate concentration = 20 rnd=1.060 mg
Adsorption Density
Adsorption
Aliquot
Chart Value
mg in
mg Adsorbed
Tirne (min-)
(mM) Solution
rng/rnmg&
0.734
5.0
0.326
1.468
6.16
2.032
Straight
1.586
0.793
5.O4
10.0
0.267
2.195
1.696
O.878
15.0
0.212
4.0 1
2.347
0.985
_ 1.897
30.0
2.1 1
O.112
2.626
0.027
2.066
0.51
1.033
60.0
2.859
2.077
1.038
120.0
0.022
0.41
2.873

I
2
3
J

5
6

&
.

bb

..
.b

b
.

Equilibrium Adsorption Of PAX On Naturai Enargite


Test Conditions
Sample weight = 0.5000 g, Solution pH = 9.0(Adjusteci with NaOH), Adsorption time = 60 min.
Botcie volume = 53.0. Agitated at 30 r.p.m. and Centrifugeci for 30 seconds
initial Conditions
Chart Value
Concenuaiion
mg in Solution
Test XantIiare
Aliquot
Conc.
No.
(mg)
(mg(l)
(mgm

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

The EfTect Of NatS On Adsorption Density Of PAX On Natural Enargite


Test Conditions
Na2S Concentration = 10.0 mg. Conditioning Time=lO min.
SampIe weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bottle volume = 53.0 ml. Agitatecl at 30 r.p.m. and Centrifugecl for 30 seconds
Initial Conditions
mg in Sotution
Chart Value Concentration
Test
Aiiquot
Xanthate
No. Concentration
(wu
(ma)

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.

Concentration = 20.0 mg/l= 1.060 mg & pH = 9.0 Modifieci With NaOH


F i Xmthate
Adsorption
Contact
Adsorption Densimg
Time
Concentration Xanthate in
(mg)

The Effect Of KMnO, On Adsorption Densi- Of PAX On Nanirai Enaqite


Test Conditions
KMn04Concentration = 50.0 m g 4 Conditioning Time=IO min.
Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH). Adsorption time = 60 min.
Bottle volume = 53.0 ml. Agitateci at 30 r.p,m. and Cenuifuged for 30 seconds
Aliquot

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.

Floatability Of Naturai Enargite


Xanthate Concentration = 20.0 m@. pH = 9.0
Time (min-)
% Recovery
NaCN Concentration
1
NaCN Concentration

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

The Effect Of NaCN On Adsorption Density Of PAX On Chalcopyrite


Test Conditions
NaCN Concentration = 15.0 rng/l. Condiioning Tme=lOxnin.
Sarnple weight = 0.5000 g, Soiution pH = 9.0 (Adjusted with NaOH),Adsorption t h e = 60 min.
Bottle voiume = 53.0 mi. Agitateci at 30 r.p.m. and Centrifuged for 30 seconds
initiai Conditions
Aiiquot
Xanthate
Chart Value Concentration
mg in Solution
Concentration
(mg0
(mgcl)
(mgn)

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

The Effect Of NazS On Adsorption Density Of PAX On Chalcopvrite

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

M O 4 Concentration = 50.0 mgA, Conditioning Tirne= 10 min.


Sample weight = 0.5000 g, Solution pH = 9.0 (Adjusted with NaOH), Adsorption tirne = 60 min.
Bottle volume = 53.O ml. Agitateci at 30 r.p.m. and Centnfuged for 30 seconds
initial Conditions
Test
Xanthate
Aliquot
Chart Value Concentration
mg in Solution
No. Concentration
(mg)
(mgm

'

(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

The Effect Of pH On Adsorption Densitv Of PAX On Chalcopvrite

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

1 The Effec Of Sodium Sulphide Concentration Aud Contact T m e On


Test No.

The Fioatabiiity Ot Chaicopvrite


.
Xanthate Concentration = 20.0 mfl, pH = 9.0
Tme (min.)
% Recavery
Na2S Concentration 1 Na$ Concentration

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

The Effect Of pH & KMnO, Concentration On The FIoatability Of


Test
o .

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

The Effect Of Aeration Conditioning On The Floatabilitv Of Chaicopyrite


Test No.
1

PAX Concentration = 20.0


Aeration Tirne (min.)
0.0

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

The Effect Of M M Concentration On The Adsoiptioo Density Of Xanthate For


Syothetic Enarglite. Natural Enargite And Chalcopyrite
Initiai Xanthate Concentration = 20.0 mg/l= 1.060 mg & pH = 9.0
Condiiioning Time = 10 minutes
Test
MAA
Final
mg Xanthate Adsorption Adsorption Density
No.
Conc.
Xanthate
in Solution
(mg)
(mg) Connmton

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

Nahirai Enargite And Chalcopyrite


Test Conditions
Sample weight = 0.5000 g, Solution pH = 9.0(Adjusteci with NaOH)
Bottle volume = 53.O mi. Agitated at 30 r.p.m. and Centrifugai for 30 seconds
MAA Concentration = 250.0 mg& M&i Condiuoning Time = 10 Min.
Initial xanthate concentration = 20.0 mgA = 1.060 mg
I ~ h a r t ~ a l u c Imgin 1
mg
1 Adsorption Density

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

The Effect Of MAA Conditioning Time On The Adsorption Density Of PAX On


Synthetic And Naturd Enargite
Initial xanthate concentration = 20.0 rngA = 1.060 mg, & pH=9.0
MAA Concentration = 250.0 mg/l
Conditioning Chart Value
mg in
mg Adsorbeci
Adsorption Density
Time
SoIution
(mgm
(minutes)

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

The Effea Of PAX Concentration On The Adsorption h i t y For Synthetic Enargit~


Naairai Enargite And Chahpyrite
MAA Concentration = 250.0 m& MAA Conditioning T i e = 10 Min,

pH = 9.0

(mg/i)

1 Solution 1

ci sorbe ci

PAX Concentration = 20.0 mg/l= 1.060 mg


Spthetic Enargite
17-70
0.938
O. 122
Naturai Enargite
15.22
0.807
0.253

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

The Effect Of MAA Concentration On The Fioatability Of Synthetic Enargite,


Naturai Enargite And Cbalcopyrite
MAA Conditioning Tie = 10.0 Mh,pH = 9.0
PAX Coacentrabon = 20.0 mg/l
Test No.
MAA Concentration 1
O/oR

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

PAX Concentration = 20.0 mg/i


1
2.
3
1

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

,
,

PAX ~oncenaa<ion2 20.0 mg& PH-=9.0


Su~fce
%R
Tension
(dyndm)

Synthetic

Nafurai

Champyrite

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