Iranian Journal of Science & Technology, Transaction B, Engineering, Vol. 31, No.

B4, pp 431-440 Printed in The Islamic Republic of Iran, 2007 Shiraz University

POTENTIAL CONTROLLED FLOTATION OF * SARCHESHMEH MOLYBDENITE M. KOLAHDOOZAN1** AND H. NOORI2

1

Dept. of Mining Engineering, University of Tehran, Tehran, 11365, I. R. of Iran 2 Yazd University, Yazd, I. R. of Iran

Abstract Molybdenite flotation in the Sarcheshmeh Copper Complex was studied as a function of pulp potential, controlled using two types of sodium sulfide, a mineral origin and a chemical nature. Air and either plant or laboratory nitrogen were used as flotation careers. Potential readings took place in rougher cells, as it was proved to be vital in the molybdenite circuit. Results showed that, at reducing potentials between -525 and -575 mv, the highest molybdenum recovery of 93% and the lowest copper recovery of 4-15% can be achieved. These potentials did not change considerably by adding extra amounts of sodium sulfide. At more oxidizing potentials, i.e. more than -450 mv, copper recovery increases while the recovery of Molybdenite drops. Keywords Flotation, molybdenite, copper sSulfides, pulp potential, sodium sulfide, sarcheshmeh copper complex

1. INTRODUCTION The majority of molybdenite production worldwide is a by-product of copper porphyry ores in which Mo grade varies between 0.01 and 0.06% and is accompanied by chalcopyrite and chalcocite. Due to the hydrophobic nature of molybdenite, it can be floated with copper sulfides. Thus the overall concentrate of Cu and Mo contains 0.2-1% of molybdenum, as well as 20-42% of copper. To separate Mo, Cu and Fe minerals depressants are used, the most important of which are sodium sulfide, sodium hydrosulfide, Anomal D (arsenic noxe), sodium cyanide, ferro-pottasium and ferro-cyanide. The first three cases have been used for porphyry ores successfully [1]. In the molybdenum plant of the Sarcheshmeh Copper Complex only sodium sulfide has been used so far. Electrochemical studies show that the recovery in the flotation of sulfides is a function of potential at the solid-liquid interface [2, 3]. Electrochemically controlled flotation has been employed for molybdenite separation from copper sulfides extensively. By adjusting pulp potential one can depress copper sulfides while floating molybdenite [4]. Also, to optimize sodium sulfide consumption, nitrogen has been used instead of air, while pulp potential was controlled simultaneously [4]. It was observed that the consumption of sodium sulfide can be lowered by 48% when nitrogen is used. Also, by controlling pulp potential, a 21% decrease in Na2S was achieved [4]. Natarajan and Iwasaki studied the effect of pulp potential by applying a platinum electrode during the Cu-Mo separation process and concluded that chalcopyrite flotation is only suitable while pulp potential is about 100 mv. In higher potentials and at a pH between 10.5 and 11.0, it was noted that xanthate adsorbs as dixanthogen [5]. The average copper grade in the Sarcheshmeh Copper Complex to be delivered to a processing unit is set at 1.2%. However there is no control applied for the grade of molybdenum which usually varies between 0.01 and 0.04%. During concentration, a Cu-Mo concentrate is produced by one stage of

Received by the editors January 4, 2006; final revised form March 3, 2007. Corresponding author

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roughing, one stage of scavenging and two stages of cleaning. The final concentrate contains 0.5% of Mo and 32% of Cu, while the particle size is 90% under 42 microns (325 mesh). Because of the high grade of Mo in this concentrate and economic interest, a molybdenite concentration plant was added to the circuit and started production in 1984. This plant was designed to receive 1432 tons of Cu-Mo concentrate (on dry basis) and consists of one stage of roughing followed by seven stages of cleaning. After dewatering the concentrate contains 53.7% Mo which is dried and shipped overseas. As the aim of this study was to obtain an optimum potential in the molybdenite flotation circuit, laboratory tests were performed using the main feed entering the plant. In order to ensure practical implications, tests were repeated in the production line as well. 2. MATERIALS AND EQUIPMENT a) Ore A representative sample was obtained from Cu-Mo thickener underflow. For each test a 30 liter sample was used. The density was set between 55-60% solid, which was diluted to 28% solid just before the tests. b) Reagents Reagents used in the flotation of Cu and Mo, including Z11 (sodium isophrophil xanthate) and R407 (a mix of dithiophosphate and mercaptobenzothiazol), have to be neutralized before floating Mo by a depressant since they can render Cu and Fe sulfides hydrophobic. For this purpose, sodium sulfide can be used as either a mineral or as a chemical product. In this study both types were used and the activity of this reagent was set as 60. Diesel fuel can be used as collector for molybdenite. Frothers such as pine oil and A65 (a propylene golycol) are contained in the feed and therefore there is no need to add them in the flotation of molybdenite. c) Nitrogen The nitrogen used in this research contained 5 ppm of oxygen and was produced locally in the Sarcheshmeh Complex laboratory. Also, a series of tests were performed using the same nitrogen as that used in the Mo plant, showing a 3-4% impurity. d) Equipment Including a Denver D12 laboratory flotation cell, laboratory filter press, pH meter, and potentiometer equipped with a Pt-Ag/AgCl electrode saturated by KCl. 3. TESTS In order to determine the circuit potential, samples were taken from the end points of each cell and potentials were measured. This was done for all flotation cells and it was observed that potential values from one connection box to the next remain constant. Therefore, in the next stage, measurements were performed on rougher cells number 1, 3 and 7, primary cleaner cells number 1 and 4, secondary cleaner cell number 1, tertiary cleaner cell number 1 and 4 and fourth, fifth, sixth and seventh stage cleaner cell number 1(Fig. 1). a) Relationship between redox potential and Na2S dosage This relationship has to be evaluated for the following cases: - When using nitrogen and non-mineral Na2S;
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- When using nitrogen and mineral Na2S; - When using air and non-mineral Na2S; - When using air and mineral Na2S. As noted, tests were performed in both the plant production line as well as the laboratory.
Feed Rougher

Primary Cleaners

Secondary Cleaners

Tertiary Cleaners 4th Stage Cleaners

5th Stage Cleaners

6th Stage Cleaners

7th Stage Cleaners

Na2S Addition Point Potential Measurement Point Fig. 1. Schematic presentation of molybdenum circuit, Na2S addition points and potential measurement points
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b) Plant tests These tests were performed in a Denver 2.5 liter flotation cell agitating at 1000 rpm. Pulp density was set at 1271 gr/lit or 28% solid. Sodium sulfide was conditioned for 1 minute and the redox potential was measured by an ORP electrode as well as a potentiometer. Either air or nitrogen was used as flotation career. c) Laboratory tests Details were the same in this case except for the source of nitrogen. d) Redox potential measurement at different points of the circuit Figure 2 shows Eh for different points in a circuit. As shown potential becomes more reducing, representing the end of the Mo flotation circuit, and thus promoting the depression of Cu and Fe minerals. It can be explained that as the circuit moves, introducing a more reducing environment can cause the desorption of the collector species from Cu and Fe mineral surfaces, and therefore, inhibit their flotation. As most of the recovery of molybdenite as well as the highest consumption of Na2S(almost 50% of the total) take place in rougher cells, the focus of this study was the potential measurements in this section of the circuit. Figure 3 shows the average potential readings for three rougher cells, number 1, 4 and 7. The results show that potential variation is between -510 and -620 mv, which means the Na2S consumption is not constant at different points of the circuit, and also the variation is substantial.
Series1 Series4 Series7
750 700 650
Eh (-mv)

Series2 Series5 Series8

Series3 Series6 average

600 550 500 450 400

cl.1-1 cl.3-4 cl.4-1 cl.3-1
1

cl.6-1

cl.7-1

Fig. 2. Potential values at different points of Mo circuit in a series of measurements

Rf1

Rf3

Eh(-mv) 620 600 580 560 540 520 500 1 2

1st Rougher

Fig. 3. Potentials in rougher cells in a series of measurements

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Rf7

cl.1-4

Measurment Points

4th Rougher

cl.2-1

cl.5-1

cl.3.1

7th Rougher

Day

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e) Redox potential versus Na2S consumption 1 In Plant: Two different set ups were considered: A 2 liter pulp was taken from a 2.5 liter flotation cell with 28% solid content. The potential was measured and then 0.1 kg/ton sodium sulfide was added and conditioned for 1 minute, after which plant nitrogen was introduced to the pulp and at equilibrium, potential was measured by an ORP electrode, as well as by a potentiometer. In the next stage a different dosage of Na2S was used and the tests repeated. The procedure was repeated for air instead of nitrogen. Results are brought in Fig. 4. As shown, potential increased toward a more reducing state as Na2S increased for up to 8 kg/ton and then stayed almost constant. Also potentials are more reducing when nitrogen was used compared to the air.
N2 700 600 500 (-)mv 400 300 200 100 0 0 5 10 15 20 2s 25 30 air

Kg/ton Na2S

kg/ton Na

Fig. 4. Potential variation vs. mineral Na2S consumption

B Potential values were measured after 1, 2 and 3 minutes. Results are shown in Figs. 5 and 6 for air and nitrogen respectively. As seen, for air the time plays a more important role as there is a considerable difference among the readings compared to the nitrogen. The reason is that nitrogen causes deoxygenation of the pulp. This stresses the advantage of using nitrogen in Mo flotation.
At first After 2min
700 600 500 400 300 200 100 0 0 5 10 15 20 kg/ton Na2 S 25 30 35

Air

After 1min After 3min

Fig. 5. Potential variations vs. mineral Na2S consumption and time effect in plant and in presence of air
At first After 2min 800 600 (-)mv 400 200 0
0 5 10 15 20 25 30 35 kg/ton Na2S

(-)mv

After 1min After 3min

Fig. 6. Potential variations vs. mineral Na2S consumption and time effect in plant and in presence of plant nitrogen
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2 - In laboratory: Figure 7 shows the result where Potential values were drawn against cumulative nonmineral Na2S dosage. As shown, only in higher dosages of sodium sulfide (around 15 kg/ton and more) potential readings equal to what was read in the plant. This is more apparent when using nitrogen.
Eh with N2 700 600 500 (-)mv 400 300 200 100 0 0 5 10 15 kg/ton Na2S 20 25 30 Eh with air

Fig. 7. Potential variations vs. non-mineral Na2S consumption and time effect in laboratory and in presence of nitrogen

Figures 8 and 9 show the time effect on potential when using non-mineral Na2S and air or plant nitrogen respectively. For air, it can be concluded that for up to 5 kg/ton sodium sulfide potential drops very fast and then the variation slows down. The reason is the oxygen content of the air that, as time passes, tends to shift potential readings more toward an oxidizing zone. The same pattern, but with a lower drop in potentials toward the oxidizing side, is observed while using nitrogen.
At first After 2min After 1min After 3min

700 600 500

(-)mv

400 300 200 100 0 0 5 10 15 kg/ton Na2S 20 25 30

Fig. 8. Potential variations vs. non-mineral Na2S consumption and time effect in laboratory and in presence of plant air laboratory and in presence of plant air

The next series of tests were performed using mineral Na2S and laboratory nitrogen and air. Figures 10 and 11 show the results. Again potential variations are greater when using air, although purer nitrogen causes even less variation compared to plant nitrogen. Table 1 lists potential readings for different cases. As seen, in more oxidizing potentials while using nitrogen, sodium sulfide consumption is very low. The best case to reach more reducing potentials is to use laboratory nitrogen and non-mineral sodium sulfide.
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Table 1. Potential readings at different types and dosages of Na2S Potential(mv) -100 -150 -200 -250 -300 -350 -400 -450 -500 -550 -600 Mineral Na2S (kg/ton) Plant N2 0.15 0.20 0.27 0.30 0.32 1.50 2.00 3.00 5.00 10.5 24.00 Lab N2 0.10 0.20 0.25 0.50 0.60 0.70 1.60 2.10 4.90 8.10 22.50 Air 0.80 1.00 1.20 1.60 2.00 3.00 4.70 6.50 8.20 14.00 --Non-mineral Na2S (kg/ton) Lab. N2 0.40 0.50 0.70 0.90 1.00 1.10 1.30 2.40 5.00 7.50 17.0 Air 0.80 0.90 1.00 1.10 1.30 1.80 2.90 3.50 5.60 10.20 23.00

At first After 2min 700 600 500 400 300 200 100 0 0 5 10 15

After 1min After 3min

(-)mv

20

25

30

kg/ton Na2S

Fig. 9. Potential variations vs. non-mineral Na2S consumption and time effect in laboratory and in presence of lab. nitrogen

At first After 2min

After 1min After 3min

700 600 500 (-)mv 400 300 200 100 0 0 5 10 15 20 25 30 35 kg/ton Na2S Kg/ton Na2S

Fig. 10. Potential variations vs. mineral Na2S consumption and time effect in laboratory and in presence of lab. nitrogen

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At first After 2min 700 600 500

Air

After 1min After 3min

(-)mv

400 300 200 100 0 0 5 10 15 20 kg/ton Na2S 25 30 35

Fig. 11. Potential variations vs. mineral Na2S consumption and time effect in laboratory and in presence of air

3. Redox potential Mo recovery and Cu, Fe depression: Figures 12 and 13 present the variation in the recovery of Mo, Cu and Fe as a result of potential change, while using nitrogen for mineral Na2S and nonmineral Na2S respectively. The highest Mo recovery in the case of using mineral Na2S, i.e.93%, can be reached at -550 mv potential. Giving a 50 mv margin for possible errors, it can be concluded that the optimum pulp potential to reach the highest Mo recovery and the lowest Cu and Fe recoveries is between -525 and -575 mv. When non-mineral Na2S was used, although there is not a considerable change in Mo recovery, better depression for Cu and Fe minerals(less than 10% recovery) are achieved. For this case too, the same optimum potential values (-525 up to -575) are suggested. According to previous tests, this potential corresponds to 10-15 kg/ton sodium sulfide consumption. The reason for better depression for Cu and Fe minerals at this potential is that it impossible for either xanthate or dixanthogen to be adsorbed on Cu and mineral surfaces at this potential. At less reducing potential, -450 mv and higher, which seems to be a critical point, these minerals can not be effectively depressed, while in more reducing potentials, less than 550 mv, in addition to Cu and Fe depression, Mo could be depressed as well.
Mo 100 90 80 70 60 50 40 30 20 10 0 350 Fe Cu

Recovery%

400

450 (-mv)

500

550

600

Fig. 12. Mo, Cu and Fe recovery vs. potential for mineral Na2S

Figure 14 shows the variation of Mo grade as a result of potential change while using non-mineral Na2S. As shown, Mo grade was increased for potentials up to -600 mv, while Cu and Fe grades remained almost the same after -500 mv. This stresses the fact that using more sodium sulfide, which causes a greater reducing condition in pulp, doesnt show any considerable effect beyond a certain point, i.e. -550 mv of potential. In the case of using mineral Na2S (Fig. 15), almost the same pattern was observed although
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beyond -550 mv there is a slight drop in Mo recovery in this case. Table 2 lists the grade and recovery data. It emphasizes the fact that the highest Mo recovery can be achieved with potentials around -550 mv for both mineral and non-mineral Na2S. However, when using non-mineral sodium sulfide, a better copper depression was observed.
Mo 100 90 80 70
Recovery%

Fe

Cu

60 50 40 30 20 10 0 350 400 450 (-mv) 500 550 600

Fig. 13. Mo, Cu and Fe recovery vs. potential for non-mineral Na2S
Mo 30 25 20 15 10 5 0 350 Fe Cu

Grade(%)

400

450 (-mv)

500

550

600

Fig. 14. Mo, Cu and Fe grade vs. potential for non-mineral Na2S Table 2. Mo and Cu recoveries in various conditions Potential (MV) -350 -400 -450 -500 -550 -600
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Mineral Na2S (kg/ton) 0.70 1.60 2.10 4.90 8.10 22.50 %R(Mo) 70.48 81.84 87.49 90.60 93.67 91.02 %R(Cu) 27.83 27.21 26.13 25.67 23.90 21.75 1.10 1.30 2.40 5.00 7.50 17.00

Non-mineral Na2S (kg/ton) %R(Mo) 71.10 78.00 86.61 90.49 92.71 91.27 %R(Cu) 26.22 25.29 25.07 21.21 18.39 18.07

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Mo 30 25 Grade(%) 20 15 10 5 0 350 Fe Cu

400

450 (-mv)

500

550

600

Fig. 15. Mo, Cu and Fe grade vs. potential for mineral Na2S

4. CONCLUSIONS 1 Potential changes in Mo rougher cells between the two connecting boxes are constant. However the potential variation in the roughing circuit is between -510 and -620 mv, which is considerable. 2 It was determined that the potential of -550 mv can be achieved while using 8.1 kg/ton mineral Na2S with nitrogen or 14 kg/ton applying air. 3 It was determined that the potential of -550 mv can be achieved using 7.5 kg/ton of non-mineral Na2S with nitrogen or 10.20 kg/ton using air. 4 The optimum potential for a 93% Mo recovery was determined as -525 mv till -575 mv. In these circumstances there is a 15% and 4% copper recovery while using mineral and non-mineral Na2S respectively. 5 To reach more reducing potentials (higher than -550 mv) there should be a considerable increase for both mineral and non-mineral Na2S consumption. While applying nitrogen to reach a-600 mv potential, mineral and non-mineral Na2S dosage consumption are 22.5 and 17 kg/ton respectively. Therefore, pulp potential of -550 mv is a high critical point to reach the best recovery for Mo, the highest depression of Cu and an optimum Na2S consumption. 6 At more oxidizing conditions(less than -450 mv), Mo recovery drops while Cu recovery increases. Thus this is a lower critical point for potential. Acknowledgements- The authors wish to express their sincere gratitude to the personnel of the Research and Development Center of the Sarcheshmeh Copper Complex for their technical and financial support. REFERENCES
1. 2. 3. 4. 5. Castro, S. (1988). Selective flotation of molybdenite: depression mechanism of chalcocite. Int. J. Min. Process., pp. 404-416. Chander, S. (2003). A brief review of pulp potential in sulfide flotation. Int. J. Min. Process., pp. 144-152. Cheng, X. & Iwasaki, I. (1992). Pulp potential and its implications to the sulfide flotation. Int. J. Min. Process., 147-156. Chander, S. & Fuerstenau, D. W. (1982). Electrochemical flotation separation of chalcocite from molybdenite. Int. J. Min. Process., pp. 42-51. Natarajan, K. A. & Iwasaki, I. (1970). Behaviour of platinum electrodes as redox potential in some systems of metallurgical interest. Mining Engineering, pp.317-324.
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