Ian Wark Research Institute

Australian Research Council Special Research Centre For Particle and Material Interfaces

Effect of polyacrylic acid in restoring chalcopyrite an molybdenite flotation

Maria Sinche Gonzalez, D. Fornasiero and M. Zanin

Water in mineral processing

Cations, anions

Process water

Dissolved gases

Organic compounds (reagents, micro-organism)

Suspended solids

Water quality in flotation

0.9 0.8

Overall recovery
0.85 0.8 0.75 0.7 0.65 0.6 0.55 0.5 0.45 0.4 0.35 0.3 0.25 0.2 0.15 0.1 0.05 0
0.5 0.6 0.7 0.8 0.9

0.7

Froth recovery

0.6

0.5

0.4

0.3

Water quality can affect both froth zone and collection zone

0.2

0.1 0.4

Collection zone recovery

Metal ions in solution may depress the sulphide minerals

- Collection Zone Issues -

Hypothesis
MI in solution can: Precipitate as hydroxide on the surface of Cp and Mo particles, reducing the overall hydrophobicity and contact angle Reduce the surface charge of Cp and Mo particles to less negative values, and promote the formation of slime coatings The addition of a charged organic dispersant (PAA) may be beneficial in preventing/reversing metal ion deposition on the surface of Cp and Mo

Metal hydroxide may form in solution at typical plant pH (9.3)

Ca2+

pH of hydroxide formation: Fe<Al<Mn

10-4 M

Mg2+ Mn2+

Al3+

Effect metal ions on flotation:

Fe3+

Fe>Al>Mn
pH of hydroxy complex formation vs metal ion concentration (Monhemius, 1977; Sandstrom, 2007)

MI may favor slime coatings on molybdenite

MoS2 is negatively charged
Zanin et Al., 2010 AMIRA P260E
MoS2+ Ca2+ MoS2 MoS2+SiO2 MoS2+Ca2++SiO2

MI adsorption reduces the negative charge and improves floatability BUT Increases potential to aggregate with negatively charged gangue particles Can dispersants counteract ??
Ca2+ adsorbed at the edges + MoS2

SiO2 Raghavan & Hsu (1984)

+
7

+ + -

Experimental approach
Single minerals: Chalcopyrite -75+38 um Molybdenite -250+150 um

amplifier computer

zeta potential
(Malvern Zetasizer Nano) 50 Hz

batch flotation

Effect of Fe, Al and Mn investigated

detachment force (related to CA)

Flotation response in the presence of MI

Chalcopyrite
100
No metal ions Fe Al Mn

Molybdenite
100
No metal ions Fe Al Mn

Cumulative Cu recovery %

60

Cumulative Mo recovery %

80

80

60

Al
40

Fe

Mn Al Fe

40

20

20

0 0 1 2 3 4 5 6 Time (min) 7 8 9

0 0 1 2 3 4 5 6 Time (min) 7 8 9

Effect of metal ions (10-4 M) on chalcopyrite and molybdenite recovery as a function of flotation time at pH 9.3 ([KNO3] =10-2 M)

lativ tive eC Cu ee ry CC uu mmuula u re r eccoovv r y%%

10

20

30

40

50

60

70

80

90

N o m e ta l io n s F e 2 x 1 0 -5 / 0 F e 2 x 1 0 -5 / 2 .1 x 1 0 -6 F e 2 x 1 0 -4 / 0 F e 2 x 1 0 -4 / 1 .1 x 1 0 -6 F e 2 x 1 0 -4 / 2 .1 x 1 0 -6 A l 2 x 1 0 -5 / 0 A l 2 x 1 0 -5 / 2 .1 x 1 0 -6 A l 2 x 1 0 -5 / 5 x 1 0 -5 A l 1 0 -4 / 0 A l 1 0 -4 / 2 .1 x 1 0 -6 A l 1 0 -4 / 5 x 1 0 -5

Chalcopyrite

Effect of metal ions and PAA in flotation

Metal ions (M) / PAA (M)

10 0
N o m e ta l io n s F e 3 x 1 0 -5 / 0 F e 3 x 1 0 -5 / 8 .2 x 1 0 -7 F e 3 x 1 0 -5 / 1 .2 x 1 0 -6 F e 1 0 -4 / 0 F e 1 0 -4 / 2 .1 x 1 0 -7 F e 1 0 -4 / 4 .1 x 1 0 -7 A l 3 x 1 0 -5 / 0 A l 3 x 1 0 -5 / 4 .1 x 1 0 -7 A l 3 x 1 0 -5 / 8 .2 x 1 0 -7 A l 1 0 -4 / 0 A l 1 0 -4 / 2 .1 x 1 0 -7 A l 1 0 -4 / 1 0 -6 M n 2 x 1 0 -5 / 0 M n 2 x 1 0 -5 / 4 .1 x 1 0 -7 M n 1 0 -4 / 0 M n 1 0 -4 / 2 .1 x 1 0 -7 M n 1 0 -4 / 4 .1 x 1 0 -7

C u m u la tiv e M o re c o v e ry %
20 30 40 50 60 70 80

Metal ions (M) / PAA (M)

Molybdenite

Effect of PAA on chalcopyrite and molybdenite recovery in presence of Fe, Al and Mn ions (pH 9.3)

Zeta potential in the presence of MI

Chalcopyrite
30 20 10
zeta potential (mV)

Molybdenite
30 20 10
zeta potential (mV)

0
(2)

0
(2) (3)

-10
(3)

-10 -20 -30 -40

(1)

-20
(1)

-30 -40 -50 -60 -70 0 1 2 3 4 5 pH 6 7 8 9 10 11

Cp Cp + PAA 10-5 M Fe(OH)3 10-4M Fe(OH)3 10-4 M + PAA 10-5 M Cp + Fe(OH)3 10-4M Cp + Fe(OH)3 10-4 M +PAA 10-5 M

-50 -60 -70 0 1

Mo Mo +PAA 10-5 M Fe(OH)3 10-4M Fe(OH)3 10-4M + PAA 10-5 M Mo + Fe(OH)3 10-4M Mo + Fe(OH)3 10-4 M +PAA 10-5 M

6 pH

10

11

Zeta potential of Mo, Cp and freshly prepared Fe(OH)3 10-4 and PAA, pH =9.3

Measurement of the detachment force

Xu et Al., 2010 AMIRA P260E

Particle-bubble detachment force: Fe nitrate and PAA

Chalcopyrite
Detachment Force (N)
3.5E-05

Molybdenite
3.0E-05

3.0E-05

Increasing collector Increasing PAA

a
2.5E-05 2.0E-05 1.5E-05 Increasing PAA

Detachment force (N)

2.5E-05

2.0E-05

1.5E-05

1.0E-05
1.0E-05

5.0E-06

5.0E-06 0.0E+00

3x10-5 / 8.2x10-07 / 0.5

6x10-5 / 8.2x10-07 / 0.5

Fe ion concentration (M)/ PAA concentration (M) / collector concentration

Detachment force for chalcopyrite and molybdenite particle-bubble in the presence of Fe nitrate and PAA, at pH 9.3 (*1= 2 g/t SIPX for CuFeS2, and *1= 22 g/t diesel oil for MoS2)

Fe ion concentration (M)/ PAA concentration (M) / collector concentration

6x10-5 / 1.2x10-06 / 0.5

2x10-5 / 2..1x10-06 / 0.5

3x10-5 / 0 / 0.5

2x10-5 / 4.2x10-06 / 0.5

6x10-5 / 0 / 0.5

2x10-5 / 0 / 0.5

0 / 0 / 0.5

2x10-5 / 0 / 0

0 / 0 / 0.5

0/0/1

0/ 0/0

0.0E+00

Particle-bubble detachment force: Al nitrate and PAA

Chalcopyrite
2.5E-05

Molybdenite
3.0E-05
b

2.0E-05

2.5E-05 2.0E-05

Increasing PAA

1.5E-05

1.5E-05
1.0E-05

1.0E-05
5.0E-06

5.0E-06
2x10-5 / 4.2x10-06 / 0.5

Detachment force for chalcopyrite and molybdenite particle-bubble in the presence of Al nitrate and PAA, at pH 9.3 (*1= 2 g/t SIPX for CuFeS2, and *1= 22 g/t diesel oil for MoS2)

Al ion concentration (M)/ PAA concentration(M) / collector concentration

Al ion concentration (M)/ PAA concentration(M) / collector concentration

6x10-5 / 8.2x10-07 / 0.5

6x10-5 / 1.6x10-06 / 0.5

0 / 0 / 0.5

2x10-5 / 0 / 0.5

2x10-5 / 6.2x10-6 / 0.5

3x10-5 / 0 / 0.5

6x10-5 / 0 / 0.5

0 / 0 / 0.5

0.0E+00

0.0E+00

Conclusions
Al and Fe ions decrease CuFeS2 and MoS2 flotation recovery, zeta potential and attachment force. Changes in zeta potential suggest adsorption/precipitation of metal hydroxide on the mineral surface of CuFeS2 and MoS2 decreasing particles hydrophobicity. PAA (polyacrylic acid) restored the flotation of chalcopyrite and molybdenite when Fe, Al and Mn were present at concentration <10-4M. PAA acts preventing the deposition of metal hydroxide. Trials on real flotation pulps will follow.

Acknowledgements
The authors acknowledge the financial support of: Australian Research Council (ARC) Sponsors of the AMIRA International P260E project

Thank you!