MANGANESE IN SX/EW PLANTS

G.ZARATE

CYTEC SEMINAR, ANTOFAGASTA, OCTOBER 2010

CONTENTS * INTRODUCTION * REVIEW OF MANGANESE PROBLEMS * PROPOSED CONTROL MEASURES * CHEMICAL REACTIONS * ACTUAL DATA * CONCLUSIONS

INTRODUCTION The occurrence of significant concentrations of Mn in PLS is common in Chile and other countries. The literature of its effects on industrial plants is sparse and some recommendations has no back up. Only five operations have been reported in the past as suffering effects from Mn in PLS: * Tyrone * Chino * Johnson Camp * Chuquicamata * Girilambone Of these, only Chuquicamata and Girilambone have published the results of their experience.

REVIEW OF MANGANESE PROBLEMS Mn+2 itself has no effect on SX operation. It is transferred by aqueous entrainment to the electrolyte. Once in the electrolyte, it can be oxidized to higher oxidation states. Particularly noticeable at low iron concentrations. Some of the problems that have been associated to the high oxidation state of Mn (Mn+7 and/ore Mn+3) are:

* Deposition of black MnO2 inside the cells * Purple colouration of cell electrolyte OF (MnO4(MnO4-) * Chlorine gas evolution * Oxidation of SX reagent and accumulation of reaction products in the organic phase * Increased corrosion of stainless steel components

 The effect on anode corrosion is as follows( RSR information): * Manganese attacks the PbO2 layer and causes MnO2 to build up in the layer. MnSO4 + PbO2 PbSO4 + MnO2 * The PbSO4 is converted back to PbO2, but it is now deposited in loose layers. * These layers are easily spalled off causing contamination of the copper cathode.

12

10

Corrosion Rate (g/kAh)

2 0 50 100 150 200 250 300 350 400

Manganese concentration (ppm)

12

10

Corrosion Rate (g/kAh)

2 0 2 4 6 8 10 12

Iron concentration (g/l)

PROPOSED CONTROL MEASURES Reducing the PLS entrainment by: * Using coalescers and/or wash stages * Reducing crud generation Maintaining manganese as Mn+2 by using: * A minimum ratio of 8:1 or 10:1 (Fe:Mn). * A minimum concentration of 1 g/l Fe. * A minimum Fe+2/Mn ratio of 6:1.

CHEMICAL REACTIONS The overall reaction for the electrochemical deposition of MnO2 is: Mn+2 + 2 H2O MnO2 + 4 H+ + 2 e It occurs in several steps and there are several differing theories: * MnO4- involved in the initial precipitation of MnO2 on the anode. * Through adsorbed species such as MnOOH and also by disproportionation of Mn+3 Manganese dioxide can also form directly in the electrolyte as slimes. (1)

 Other possible reactions: Mn+2 Mn+3 + e(2)

Mn+2 + 4 H2O MnO4- + eMnO4- + 4 Mn+2 + 8 H+ 5 Mn+3 + 4 H2O 2 Mn+2 + PbO2 + HSO4- + 3 H+ 2 Mn+3 + PbSO4 + 2 H2O

(3)

(4)

(5)

 Mn+3 is unstable, except in very concentrated acid solutions and disproportionate by reaction 2 Mn+3 + 2 H2O MnO2 + Mn+2 + 4 H+ (6)

MnO4- is metastable and could only be observed at low concentration of Mn+2 and high potentials.

 To maintain manganese as Mn+2, the most used reaction is: MnO4- + 5 Fe+2 + 8 H+ Mn+2 + 5 Fe+3 + 4 H2O It can also react with chloride: 2 MnO4- + 8 H+ + 6 Cl- 2 MnO2 + 4 H2O + 3 Cl2 (8) (7)

ACTUAL DATA Mn in Electrolyte (Cu 2003)

Plant El Abra MV Andacollo Cananea Nacozari Toquepala Cerro Verde Tyrone Chino Morenci Nifty Mt. Cuthbert Mn (ppm) 38 40 60-100 26 300 100 70 <100 150-350 40 90 80

900

800

700

600 Planta Planta Planta Planta Planta Planta 1 2 3 4 5 6

Mn (ppm)

500

400

300

200

100

0 Oct-06

Abr-07

Nov-07

Jun-08

Dic-08 Month

Jul-09

Ene-10

Ago-10

Feb-11

* Fe in electrolyte
8,0

7,0

6,0

5,0 Fet (gpl)

4,0

3,0

Planta Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6 7

2,0

1,0

0,0 Oct-06

Abr-07

Nov-07

Jun-08

Dic-08 Month

Jul-09

Ene-10

Ago-10

Feb-11

* ClCl- in the electrolyte

80

70

60

50 Planta Planta Planta Planta Planta Planta 1 2 3 5 6 7 Cl- (ppm)

40

30

20

10

0 Oct-06

Abr-07

Nov-07

Jun-08

Dic-08 Month

Jul-09

Ene-10

Ago-10

Feb-11

* Redox (mV/SHE)
1000 900

800

700

Redox (m V/SHE)

600

500

400

Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6

300

200

100

0 0,0 5,0 10,0 15,0 20,0 Fe+2/Mn 25,0 30,0 35,0 40,0

1000

900

800

700

Redox (mV/SHE)

600

500

400

300

200

100

0 0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0 8,0 9,0 Fe++/Mn 10,0 11,0 12,0 13,0 14,0 15,0 16,0 17,0 18,0

1000

900

800

700

Redox (mV/SHE)

600

500

400

Planta Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6 7

300

200

100

0 0,0 1,0 2,0 3,0 4,0 Fet (gpl) 5,0 6,0 7,0 8,0

1000

900

800

700

Redox (mV/SHE)

600

500

400

Planta Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6 7

300

200

100

0 0 5 10 15 20 25 Cl- (ppm) 30 35 40 45 50

1.000

950

900

850

Redox (mV/SHE)

800

750

700

Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6

650

600

550

500 0 100 200 300 400 500 600 700 800 900 Mn (ppm)

1.000

950

900

850

Redox (mV/SHE)

800

750

700

Planta Planta Planta Planta Planta Planta

1 2 3 4 5 6

650

600

550

500 0 50 100 150 Mn (ppm) 200 250 300

CONCLUSIONS The information of the effects of Mn on EW operation is sparse and some of the recommendations has no back up. The recommendations of a minimum ratio of Fe/Mn = 8 or 10 and Fe+2/Mn = 6 are not applicable. Redox potential is affected by Mn, Fe and ClCl- concentration.

 The highest redox potentials are obtained when Mn is < 10 ppm combined with a ClCl- concentration >30 ppm and Fe <2 gpl. Iron is essential to keep a lower redox potential. The recommended concentration will depend on Mn and ClClconcentration. It can be 0.5 gpl for ClCl- < 30 ppm and Mn > 20 ppm and as high as 2 gpl and more for Mn<10 ppm and ClCl->30 ppm.