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Minerals Engineering xxx (2012) xxx–xxx Contents lists available at SciVerse ScienceDirect Minerals Engineering
Minerals Engineering xxx (2012) xxx–xxx Contents lists available at SciVerse ScienceDirect Minerals Engineering

Contents lists available at SciVerse ScienceDirect

Minerals Engineering

journal homepage: www.else vier.com/loc ate/mineng Prediction of flotation behavior of sulphide ores by

Prediction of flotation behavior of sulphide ores by oxidation index

Ozlem Bicak , Zafir Ekmekci

Hacettepe University, Mining Engineering Department, 06800 Beytepe, Ankara, Turkey

article info

Article history:

Available online xxxx

Keywords:

Froth flotation

Oxidation

Sulphide ores

abstract

In addition to size, density, composition and mineralogy (mineral type, texture, liberation, etc.), surface characteristics of sulphide minerals affects flotation behavior of sulphide ores considerably. The variations

in surface characteristics of sulphide minerals can be related to the variations to the degree of surface oxidation which is known to influence the flotation performance. Surface oxidation affects dissolution behavior of sulphide minerals, activation/depression and adsorption of collectors, i.e. their flotation behav- ior. Therefore, a methodology, called ‘‘Oxidation Index’’ was developed to measure surface oxidation of sulphide minerals quantitatively and predict flotation behavior of different ore types. The methodology is based on derivation of an ore specific calibration curve and prediction of flotation performance of differ- ent ore types from the same deposit by using the calibration curve. The results of the test works performed

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using a complex Cu–Zn sulphide ore from Çayeli Bakır Is letmeleri A.S ., Turkey are discussed in this paper.

2012 Published by Elsevier Ltd.

1. Introduction

Mineralization in sulphide ore deposits is generally not homog- enous. In the same ore deposit, it is likely to observe ore types with different mineralization, different degree of liberation and also sur- face oxidation ( Ekmekci et al., 2010; Bojcevski et al., 1998; Vink, 1997; Jones, 1987 ). These variations affect flotation performance significantly depending on the structure of ore. In most of the sul- phide ore flotation plants, chemical and mineralogical properties of the flotation feed are periodically measured to control the flotation process. However, it is likely to observe drastic changes in the flo- tation response with the same chemical and mineralogical charac- teristics. This is generally attributed to the changes in surface properties of the sulphide minerals in the ore due to surface oxida- tion. Therefore, measurement of surface oxidation of sulphide min- erals has a crucial importance for plant control. Flotation of sulphide ores are strongly affected by chemical parameters like pH, Eh, dissolved ions and surface oxidation. Low degree of surface oxidation may enhance the flotation of sulphide minerals by form- ing surface coatings of metal deficient sulphides ( Buckley and Walker, 1988 ), elemental sulphur ( Trahar, 1984 ) or polysulphides ( Luttrell and Yoon, 1984 ). However, extensive surface oxidation generally reduces flotation recovery and selectivity ( Senior and Trahar, 1991; Smart, 1991 ) by coating the surface of the minerals with hydrophilic and stable metal oxide/hydroxide species. Oxidation of sulphide ores may occur due to weathering process during formation, mining, stockpiling, crushing, milling or flota- tion. In literature there has been many techniques used to

Corresponding author. Tel.: +90 3122977600/145; fax: +90 312992155. E-mail address: obicak@hacettepe.edu.tr (O. Bicak).

0892-6875/$ - see front matter 2012 Published by Elsevier Ltd.

determine the degree of oxidation which are basically Eh ( Baker et al., 1991 ), dissolved oxygen demand test ( Houot and Duhamet, 1990), EDTA extraction technique ( Rumball and Richmond, 1996; Kant et al., 1994 ), XPS and Auger surface analysis ( Smart, 1991 ), optical mineralogy, infrared spectroscopy, flotation, contact angle and zeta potential. However, most of these techniques have some limitations particularly in plant scale applications. Ethylene diamine tetra acetic acid, widely abbreviated as EDTA is a polyamino carboxylic acid and a colorless, water-soluble solid acetate. EDTA has the ability to dissolve and form complex with the oxidation products of sulphide minerals, however does not react with metal sulphides ( Shannon and Trahar, 1986; Grano et al., 1988; Rumball and Richmond, 1996 ). EDTA extraction was found to be the most suitable method for measurement of surface oxidation both in laboratory and plant scale applications ( Bicak et al., 2008 ). Therefore, the aim of this work was to develop a new measure based on EDTA extraction technique to determine the degree of oxidation of sulphide ores quantitatively. The surface oxidation as measured by the new methodology was then related to the changes in flotation performance.

2. Materials and methods

2.1. Material

In this paper, a copper–zinc massive sulphide complex sulphide

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ore from Çayeli Bakır Is letmeleri A.S ., Turkey, containing about 70%

sulphide minerals is used. The average composition of the ore are given in Table 1 .

Please cite this article in press as: Bicak, O., Ekmekci, Z. Prediction of flotation behavior of sulphide ores by oxidation index. Miner. Eng. (2012), http://

2 O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx In Çayeli ore, chalcopyrite,

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O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx

In Çayeli ore, chalcopyrite, pyrite and sphalerite are the main sulphide ore minerals. In addition to that bornite, galena and chal- cocite are found in variable proportions in different ore types in the same deposit.

2.2. Experimental methods

2.2.1. EDTA extraction test

There are many techniques to measure degree of oxidation in literature but among these techniques, EDTA extraction was found to be the most suitable for plant applications ( Bicak, 2011 ). In the EDTA extraction technique, 10–20 g of dry sample is added into a beaker containing 200 ml of 3% EDTA solution at pH 7.5 and stirred vigorously for 30 min. The beaker is sealed during extraction to prevent contact with atmosphere. After the extrac- tion, the pulp is filtered to separate the solution and the solid for chemical analysis. 3% EDTA solution was used as a standard solution in all of the tests. pH of the solution was adjusted to 7.5 with NaOH to prevent the formation of metal–EDTA precipitates ( Rumball and Richmond, 1996 ). Degree of oxidation is evaluated based on two methods of cal- culation, Es and Em. Es ( Kant et al., 1994 ) represents the amount of metal oxidized on the mineral surface which is accepted as an indication for mineral oxidation, whereas Em (Eq. (1) ) value repre- sents oxidation degree of the ore in total. In this paper, all evalua- tions are made on the basis of Em Total values.

Em ðCu; Zm; Fe Þ ¼ Amount of metal in solution ð mgÞ ðCu; Zn ; FeÞ

Amount of solid ðgÞ

ð 1Þ

2.2.2. Flotation tests

Flotation tests are conducted in a 3 l modified Leeds type flota- tion machine. Flotation feed is ground at 60% w/w pulp density for 15 min to obtain particle size 80% passing 38 l m. Aerophine (3418A) and MIBC obtained from Çayeli flotation plant were used as collector and frother respectively. The flotation tests were per- formed at 30% w/w pulp density and pH 11.5 by adding CaO to the mill. The flotation products were assayed for Cu, Zn and Fe using AAS. Flotation rate constants calculated by using first order flotation rate equation.

3. Optimization of EDTA extraction test

Factorial design was used to test the influence of different parameters in the optimization tests and the results were evalu- ated by using Design Expert 7.1.5. Surface area of the different size fractions was measured using BET technique. Fig. 1 shows the change of Em Total (mg/g) values according to the changes in extraction time and P80 passing size of material. Em Total values changes as a function of extraction time and particle size. The results of EDTA extraction tests showed that the particle size (surface area) was a significant parameter determining the amount of extracted metal from the mineral surface ( Bicak,

Table 1 Mineralogical and chemical characteristics of a typical Çayeli ore.

Mineral

(%)

Element

(%)

Chalcopyrite

7

Cu

3.5–4

Bornite

0.4

Zn

5–7

Sphalerite

12.72

Fe

28–30

Pyrite

60

Pb

0.5–1.2

Galena

0.6

Others

19.28

6 106 Micron 5 Micron 75 Micron 38 4 3 2 1 0 0 50
6
106 Micron
5
Micron
75
Micron
38
4
3
2
1
0
0
50
100
150
Em Total (mg/g)

Extraction Time (min)

Fig. 1. The changes in Em Total values with extraction time and P80 values of solid used. (P80: 80% of material passing size).

2011). Therefore, the equations used to calculate Es Cu and Em to- tal were modified to include surface area (Eqs. (2)–(4)).

Es Cp ðmg= m 2 Þ ¼ Cu Extracted ðmgÞ

Cp ð mgÞ BET ð m

2

=gÞ

Em total ¼ Em Cu þ Em Zn þ Em Fe

Em Total BET ¼

EmTotal

BET surface area ð m 2 = gÞ

ð

ð

ð

2Þ

3Þ

4Þ

In the calculation of Es Cp, chalcopyrite was assumed as the

only copper mineral in the ore. Similar calculations can be done for the other minerals (sphalerite, galena, pyrite, etc.) by using the concentrations of the other metals (Zn, Pb, Fe, etc.). Em Total can be calculated as the ratio of total amount of dissolved metal by EDTA to the amount of ore used in the extraction and unit sur- face area (Eq. (4)). Another significant parameter for extraction is the time of extraction. Fig. 1 shows clearly that even after two hours, the Em Total values continue to increase linearly. Similar finding is com- patible with literature. According to Rumball and Richmond (1996), complete dissolution of iron takes eight hour. Therefore for practical reasons, the extraction time was taken as 30 min and kept constant for all experiments. Particle size which is 80% 38 l m (also flotation size in the plant) were also kept constant

in all tests.

4. Derivation of Oxidation Index

There has been many research works in the literature investi- gating the effects of surface oxidation on flotation performance. Some of these techniques are qualitative or at best semi-quantita-

tive and does not give a quantitative index representing the degree

of oxidation of a sulphide ore. Therefore, a quantitative measure-

ments method is required to establish the relationship between oxidation and flotation performance of a given ore. Flotation tests were conducted in a 3 lt modified Leeds flotation machine. The flotation tests were performed at pH 11.5 and 30% w/

w pulp density. 15 g/t MIBC was used in the experiments, the col-

lector dosage was determined according to the copper content of the feed. Air rate is adjusted to 3 lt/min and the flotation time is 0.5–1.5 – 7 min. The products of the flotation tests were analyzed for Cu, Zn and Fe. Flotation rate constants calculated by using first order flotation rate equation (Eq. (5)).

R

¼ R 1 xð 1 e kt Þ

ð 5Þ

where, R is the Flotation Recovery (%), R 1 the Flotation Recovery at infinity (%), k the Flotation rate constant (1/min), t is the Flotation Time (min).

Please cite this article in press as: Bicak, O., Ekmekci, Z. Prediction of flotation behavior of sulphide ores by oxidation index. Miner. Eng. (2012), http://

O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx 3 For this purpose, ‘‘Oxidation

O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx

3

For this purpose, ‘‘Oxidation Index (OI)’’ is developed to deter- mine the degree of oxidation of an ore in terms of percentage (%) as given in the following equation.

OI ð %Þ ¼ Em Total BET Em Total BET min

Em Total BET max Em Total BET min

100

ð 6Þ

where; Em Total BET is the Em Total value of a studied ore that has a random oxidation degree, Em Total BET min the Em Total value of ore that has minimum oxidation degree, Em Total BET max is the Em Total value of ore that has maximum oxidation degree. Em total values for min and max oxidation conditions are re- quired to derive an oxidation index and calculate oxidation degree in percentage. For this purpose, a calibration curve is derived by oxidizing the ore to different levels artificially using hydrogen peroxide. For derivation of the calibration curve, an ore sample with good flotation response was selected from the Çayeli ore deposit. The representative samples from the ore were ground in a ring mill to obtain a product of 80% 38 l m, which is also flotation particle size for Çayeli ore. Then, the ore was treated in different concentra- tions of peroxide solutions (0%, 1%, 5%, 10%, 25%, 50%, 75% and 100%) overnight to obtain ore samples having different degree of surface oxidation. In order to obtain EDTA extraction result of an unoxidized sample, a fresh ore sample was subjected to EDTA washing prior to flotation test acid washing or ultrasonic treatment can also be used as an alternative method to remove the oxidized species from the surface of the minerals. The variation of Oxidation Index (OI) is given in Fig. 2 as a func- tion of peroxide concentration for both copper minerals and the to- tal sulphide minerals in the ore. The change in the degree of oxidation was small up to 10% peroxide concentration, and in- creased rapidly up to 50% peroxide treatment which gave 80% OI. Higher concentrations of peroxide oxidized the sulphide minerals completely.

5. Prediction of flotation performance using Oxidation Index

The relationship between cumulative copper recovery, flotation rate constant and peroxide concentration is given in Fig. 3 . Both the recovery and flotation rate of the copper minerals decrease expo- nentially with the peroxide concentration. However, the flotation recovery decreased to values lower than 5% after 50% peroxide concentration. This shows that the ore is oxidized almost com- pletely at this concentration. The relationships between Oxidation Index and copper recovery and flotation rate of the copper miner- als in Çayeli ore are illustrated in Figs. 3 and 4 respectively. In these figures, the legend ‘‘Cp’’ represents the oxidation index based on surface oxidation of the copper minerals, ‘‘Ore’’ represents the oxi- dation index based on surface oxidation of all of the sulphide min- erals in the ore. The results showed that copper recovery decreased

100 2.0 80 Kümülatif Bakır Verimi (%) Cumulative Cu Rec. (%) 1.5 60 k kCu
100
2.0
80
Kümülatif Bakır Verimi (%)
Cumulative Cu Rec. (%)
1.5
60
k kCu Cu
1.0
40
0.5
20
0
0.0
0
20
40
60
80
100
Cu Recovery (%)
k cu (min -1 )

Peroxide Concentration (%)

Fig. 3. The variations in recovery and flotation rate constant of the copper minerals as a function of peroxide concentration.

100 Cp 80 Ore 60 40 20 0 0 20 40 60 80 100 Copper
100
Cp
80
Ore
60
40
20
0
0
20
40
60
80
100
Copper Recovery (%)

OI

Fig. 4. The relationship between oxidation index and copper recovery on mineral and ore basis.

exponentially as a function of oxidation index. However, the flota- tion rate constant of the copper minerals changes linearly as shown in Fig. 5 Flotation response of the copper minerals was af- fected slightly up to a certain degree of surface oxidation, which was about 10% in terms of oxidation index value. Higher values the flotation performance decreased drastically and the sulphide minerals in the ore were almost completely depressed at OI values greater than 75%. The results showed that, the variation in flotation response of the Çayeli ore could be demonstrated as a function of oxidation index and the suggested curves represented in Figs. 3 and 4 could be used as the calibration curves to estimate flotation performance of ore samples from different parts of the ore body.

5.1. Prediction of ore variability

In order to test the flotation performance prediction capability of the Oxidation Index methodology, ten different ore types having different mineralogy and chemical composition were obtained

100 80 60 40 Cp Cp 20 Ore Cevher 0 0 20 40 60 80
100
80
60
40
Cp Cp
20
Ore Cevher
0
0
20
40
60
80
100
Peroxide Concentration (%)
OI (%)

Fig. 2. The relationship between oxidation index (OI) and peroxide concentration.

2.0 Cp Cp 1.5 Cevher Ore 1.0 0.5 0.0 0 20 40 60 80 100
2.0
Cp Cp
1.5
Cevher Ore
1.0
0.5
0.0
0
20
40
60
80
100
k Cu (min -1 )

OI (%)

Fig. 5. The relationship between oxidation index and flotation rate constant on mineral and ore basis.

Please cite this article in press as: Bicak, O., Ekmekci, Z. Prediction of flotation behavior of sulphide ores by oxidation index. Miner. Eng. (2012), http://

4 O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx from Çayeli mine. The

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O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx

from Çayeli mine. The chemical composition of the ore samples are given in Table 2 . Chemical and mineralogical composition of the ores were very different from each other. Mineralogical analysis of the ores was performed using the optical microscopy equipped with Clemex im- age analysis system. The results showed that the main copper min- eral was chalcopyrite ( Fig. 6 ) for the ores with low copper content, and in addition to chalcopyrite the secondary copper minerals mostly bornite and chalcocite were found in the ores with high copper content. The other important sulphide minerals were sphal- erite and pyrite. Degree of oxidation of each ore was determined by the EDTA extraction tests as described in Section 2.2 . The samples for EDTA extraction tests were prepared by dry grinding in a ring mill to ob- tain the flotation particle size (P80:38 micron) and surface area val- ues were determined, accordingly. Degree of oxidation of the ores was determined based on the oxidation index derived from Em val- ues, i.e. on ore basis. The results showed that the oxidation index of the ores was different from each other, changing between 3% and 72% ( Figs. 7 and 8 ). This was attributed to both the differences in surface oxidation and also their mineralogical characteristics. Batch flotation tests were conducted to determine the flotation performance of each ore type and establish the relationship be- tween the oxidation index and flotation performance. As it was shown in Table 2 , Cu content of the ores varies from 1.47% to 16.30%. Hence, the collector dosage for the copper flotation was added according to their copper contents. Ores divided into three groups according to their copper contents and the collector dos- ages added accordingly at 30, 60 and 90 g/t ( Bicak, 2011 ). The rela- tionship between the oxidation index and flotation recovery and rate constant of copper are illustrated in Figs. 7 and 8 , respectively. The solid curves given in the figures represent the calibration curve derived for Çayeli ore as described in the previous section. Both flotation recovery and rate of the copper minerals de- creases with oxidation index. The results showed that the oxida- tion index derived for Çayeli copper ore can be used successfully to predict flotation response of different ore types from the same deposit. This suggests, it will be possible to predict the flotation performance by performing an EDTA extraction test using ore sam- ples from flotation feed, stock piles or from drill cores to determine degree of oxidation quantitatively. This would help the plant met- allurgist to plan the blending strategy and take necessary precau- tions for plant performance optimization.

5.2. Plant scale studies in Çayeli flotation plant

As it was explained in the previous sections, it is possible to pre- dict floatability of sulphide ores by using the Oxidation Index methodology. Hence, the methodology was tested using the sam- ples taken from the stockpile and also flotation feed of the plant for five days. The calibration curve derived for Çayeli ore was used to predict the flotation performance.

Table 2 Chemical analysis of the ore samples from Çayeli Cu–Zn ore deposit.

Sample code

%Cu

%Zn

%Pb

%Fe

Ore 1

15.55

5.47

0.18

29.29

Ore 2

16.30

5.25

0.14

24.48

Ore 3

2.59

5.40

0.10

24.74

Ore 4

1.47

8.39

0.41

31.46

Ore 5

1.89

9.09

0.32

42.63

Ore 6

14.92

6.55

0.16

31.15

Ore 7

7.11

7.38

0.02

28.38

Ore 8

2.56

3.76

0.12

27.09

Ore 9

10.42

5.68

0.07

30.69

Ore 10

8.56

8.77

0.07

40.70

100 0.30 90 0.25 80 70 0.20 60 50 0.15 40 0.10 30 20 0.05
100
0.30
90
0.25
80
70
0.20
60
50
0.15
40
0.10
30
20
0.05
10
0
0.00
Ore 1
Ore 2
Ore 3
Ore 4 Ore 5
Ore 6
Ore 7
Ore 8
Ore 9 Ore 10
Bornite
Sphalerite
Chalcopyrite
Pyrite
Chalcocite
% Distribution of Cp, Sp, Bn, Py
% Distribution of Chalcocite

Fig. 6. Mineralogical distribution of sulphide minerals.

100 90 80 70 60 50 40 30 20 10 0 0 20 40 60
100
90
80
70
60
50
40
30
20
10
0
0
20
40
60
80
100
Cu Recovery (%)

OI (%)

Fig. 7. The relationship between cumulative copper recovery and oxidation index for the ore samples from Çayeli.

2 1.5 1 0.5 0 0 20 40 60 80 k Cu (min -1 )
2
1.5
1
0.5
0
0
20
40
60
80
k Cu (min -1 )

OI (%)

Fig. 8. The relationship between flotation rate constant ( k ) and oxidation index for the ores from Çayeli.

100 80 April 2009 60 June 2010 40 Calibration Curv 20 0 0 20 40
100
80
April 2009
60
June 2010
40
Calibration Curv
20
0
0
20
40
60
80
100
Copper Recovery (%)

OI (%)

Fig. 9. Compatibility of the calibration curve with the results of the EDTA tests conducted in the plant by Çayeli staff.

Please cite this article in press as: Bicak, O., Ekmekci, Z. Prediction of flotation behavior of sulphide ores by oxidation index. Miner. Eng. (2012), http://

O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx 5 Table 3 Chemical composition

O. Bicak, Z. Ekmekci / Minerals Engineering xxx (2012) xxx–xxx

5

Table 3 Chemical composition of the seven ores from different stockpiles that compose the flotation feed and the flotation feed in Çayeli flotation plant.

Date

Stockpile No.

Chemical composition

 
 

Cu%

Zn%

Pb%

21.04.2009

Flotation feed

3.60

3.11

0.07

22.04.2009

1ÇT

4.22

2.33

0.07

23.04.2009

3ÇT

2.88

5.88

0.18

24.04.2009

7ÇT

1.87

0.64

0.03

24.04.2009

7KP

1.79

1.84

0.04

15.06.2010

Primary ball mill feed

3.41

7.36

0.36

15.06.2010

3ÇT

3.15

13.83

0.81

15.06.2010

8ÇT

0.82

12.20

0.30

15.06.2010

5ÇT

3.25

14.38

0.89

18.06.2010

Primary ball mill feed

3.49

6.65

0.35

18.06.2010

1KP

4.42

2.27

0.05

18.06.2010

3KP

3.56

10.75

0.63

18.06.2010

6KP

4.50

6.50

0.25

18.06.2010

7KP

2.47

9.00

0.50

Fig. 9 shows the results of the Oxidation Index tests with the calibration curve for Çayeli ore. It is clearly shown that the results of the EDTA extraction tests performed in the plant are in good cor- relation with the calibration curve. These results proves that it is possible to predict flotation performance of sulphide ores by using ‘‘oxidation index’’ methodology within an acceptable accuracy as expected. A similar study was conducted by the plant metallurgists for longer period. Ore samples were collected between 15 and 18 June 2010 from different ore types in the stockpile and flotation feed to validate the methodology and test the compatibility of the calibra- tion curve and the measured degree of oxidation values. The chem- ical analysis of the ores used in this study are given in Table 3 . The oxidation index derived for the Çayeli copper ore can be used successfully to predict the flotation response of different ore types from the same deposit.

6. Conclusions and recommendations

Effects of surface area (particle size) and extraction time were found to be as important parameters for the EDTA extraction. The amount of oxidized material on mineral surfaces increases proportional with the increases in the surface area and extraction time. Therefore, the equations were modified to include surface area at constant extraction time. ‘‘Oxidation Index’’ methodology was developed to express de- gree of oxidation quantitatively. In this methodology, the ore is oxidized artificially to different degree of oxidation by using hydro- gen peroxide solutions. Based on the EDTA extraction tests applied to the artificially oxidized samples, the degree of oxidation is ex- pressed in terms of percentage (oxidation index, %) and related to flotation performance. The relationship between oxidation index and flotation recovery and rate is used as the calibration curve for prediction of flotation performance of an unknown ore sample from the same deposit. Therefore, the ‘‘Oxidation Index’’ methodol- ogy can be used to predict flotation performance of the ore types before they are fed to the flotation plant. Ore blending and also flo-

tation conditions can be modified according to the OI values deter- mined by a simple and quick test. The ‘‘Oxidation Index’’ methodology was tested by using Çayeli Cu–Zn complex sulphide ore (high sulphide mineral content). It was possible to predict flotation response of different ore types with an acceptable accuracy. This work proved that the Oxidation Index methodology is an effective tool to predict flotation response of different ore types in plant operation. However, more work is required to improve the methodology for prediction of floatability on a size by mineral basis. So that the ‘‘Oxidation Index’’ can be included as an ore parameter to the ‘‘Floatability Component Model’’. A patent (Application Number: PCT/IB11/052707) application for Oxidation Index methodology has been applied and Cayeli Cop- per Mine has started to use this technique as a standard diagnostic tool.

Acknowledgments

The authors gratefully acknowledge technical and financial sup-

_

port of Çayeli Bakır Is letmeleri A.S . and financial support of The Sci-

entific and Technological Council of Turkey (TÜB ITAK) Project No:

107M275.

_

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