New Developments in the Treatment of Sulphides

David Dreisinger University of British Columbia Vancouver, Canada

Outline
Where have we come from? a selected history
What has been happening recently?

Where might we go in the future?

Focus on Copper

Where have we been?

Copper
Chloride leaching of copper CLEAR Process and BHAS Process Heap leach SX-EW for oxides and secondary sulphides Ammonia leaching of copper - Escondida Process (Coloso) and Arbiter Process Nitrogen species catalyzed leaching of copper (NSC) Mount Gordon Copper Process Total Pressure Oxidation Process (Bagdad and Kansanshi) Medium Temperature Pressure Leach Process (Morenci) BIOCOP Process for Copper (Chile) CESL Copper Process (UHC Plant in Brazil)

Heap Leach Pad Under Preparation

Heap Leach Under Irrigation

SX-EW Mixer Settlers and Tank Farm

Copper Electrowinning Tankhouse

BIOCOP Plant Overview

Bagdad Demonstration Plant (Total Oxidation)

Where have we come from?

Base metal and precious metal innovations Necessity (Mt. Gordon, Sepon, Cobre Las Cruces) and Opportunity (Total POX at Bagdad) Successful application of hydromet unlike non-sulphides. Many unique plants Enabled by other technologies
Solvent extraction Ion exchange Electrowinning Hydrogen reduction of metals Bioprocessing Materials of construction Etc.

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Where are we going?

All the easy ores are gone (or are already being processed)? Demand for materials continues to rise (China, India, Brazil, etc.) Prices have risen which continues to make lower grade materials attractive Metallurgists have to adapt to new realities and innovate

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What has been happening recently?

New innovations in all areas Levers for innovation;
High temperature High pressure Use of catalysts (nitric/nitrous acid, chloride) Use of complexants (ammonia, chloride, etc.) Control of sulfur behaviour (surfactants) Iron precipitation chemistry Atmospheric leaching Ultra fine grinding Galvanic systems for leaching New separation and metal recovery technologies

12

Examples of Innovation
Sepon Copper Process (Laos) paper only PLATSOL Process (NorthMet Project, USA) GALVANOX Process (UBC David Dixon)

13

SEPON Copper Plant

PLATSOL PROCESS
Process developed initially for PolyMet Mining Corporation by Chris Fleming, David Dreisinger and Terry OKane

15

PLATSOL Principles
PLATSOL Process
Simple process for one-step dissolution of base and precious metals Invented at Lakefield Research Tested via Batch and Continuous Autoclave Programs at Lakefield High levels of base (+95-99%) and precious metals (9095%) recovery

Bulk Flotation (Applied to NorthMet Ore PolyMet Mining)

Pressure Oxidation: Conventional and PLATSOL Metal Extractions (220 C)

Element Cu Ni Co Conventional 99.3 95.9 >92 PLATSOL** 99.6 98.9 96

Fe
S Pt

11.5
91.5 ~0

11.5
91.5 96

Pd
Au

61.1
~0

94.6
89.4

** ACTUAL PILOT PLANT RESULTS FROM LAKEFIELD

PLATSOL Principles
Under PlatSol leaching conditions all value metals are efficiently dissolved Addition of Chloride to High Temperature Pressure Oxidation to Promote Leaching of Precious and Base Metals. PGMs, Copper, Nickel and Cobalt can then be selectively extracted The following slides show the chemistry of PLATSOL

Autoclave Leaching Base Metals

Chloride Assisted Total Pressure Oxidation Chalcopyrite Oxidation/Iron Hydrolysis: CuFeS2 + 4.25O2 + H2O = CuSO4 + 0.5Fe2O3 + H2SO4 Pyrite Oxidation: FeS2 + 3.75O2 + 2H2O = 0.5Fe2O3 + 2H2SO4 Pyrrhotite Oxidation Fe7S8 + 16.25O2 + 8H2O = 3.5Fe2O3 + 8H2SO4 Nickel Sulfide Oxidation:

NiS + 2O2 = NiSO4

Basic Ferric Sulfate Formation: Fe2O3 + 2H2SO4 = 2Fe(OH)SO4 + H2O

Autoclave Leaching Precious Metals

Gold Oxidation/Chlorocomplex Formation: Au + 0.75O2 + 4HCl = HAuCl4 + 1.5H2O Platinum Oxidation/Chlorocomplex Formation: Pt + O2 + 6HCl = H2PtCl6 + 2H2O Palladium Oxidation/Chlorocomplex Formation: Pd + 0.5O2 + 4HCl = H2PdCl4 + H2O

Temperature of 220 to 230 C.

Barren solids washed and discarded

PLATSOL Principles
Eh (Volts) 2.0 1.8

1.6
1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 0 2 4 6 pH 8 10 12 14

AuCl4Au(OH)3

Au

Eh pH Diagram for the Au-Cl system at 25 C. [Au] = 0.00001 M. [Cl] = 0.2 M.

PLATSOL Principles
Eh (Volts) 2.0 1.8 1.6 1.4 1.2 1.0

PdCl+

PdO

0.8
0.6 0.4 0.2 0.0 0 2 4 6 pH 8 10 12 14

Pd

Eh pH Diagram for the Pd-Cl system at 25 C. [Pd] = 0.00001 M. [Cl] = 0.2 M.

PLATSOL Principles
Eh (Volts) 2.0

1.8
1.6 1.4

PtCl6-2 PtO2

1.2
1.0 0.8 0.6

0.4
0.2 0.0 0 2

Pt

PtO

6 pH

10

12

14

Eh pH Diagram for the Pt-Cl system at 25 C. [Pt] = 0.00001 M. [Cl] = 0.2 M.

Optimization Tests

Optimization Tests

PLATSOL Principles
Base Metal Recovery Copper Copper Solvent Extraction and Electrowinning to Produce LME Grade Copper Metal Cathode Nickel/Cobalt Variety of Processes Possible Mixed Hydroxide Precipitation of Nickel and Cobalt Nickel and Cobalt Hydroxide Refined Off Site SX-EW or SX-Hydrogen Reduction to Metal

PLATSOL Principles

Precipitation of Precious Metals

____________________________________________ Au Pt Pd ____________________________________________ Autoclave solution (mg/L) 0.32 0.34 1.23 Product solution (mg/L) 0.01 0.00 0.01 Precipitate ( g/t) 92 102 484 Precip. Efficiency % 97 ~100 99 ____________________________________________ * Precipitation with sodium hydrosulfide

Overall Process

Applications to Other Cu/Ni/PGM Concentrates

Applications to Other Cu/Ni/PGM Concentrates

Applications to Other Feeds

Cu/Au concentrates Refractory Au Concentrates Cu/Ni/PGE mattes Pt Laterites Automobile catalysts

Other Applications
Cu - Au concentrate
(28.9% Cu,5.8 g/t Au) PLATSOLTM recovery
99.7% Cu 95.9% Au

No cyanide!

Other Applications
Refractory Au ores-concentrates (non-preg robbers)

FeS2 - FeAsS conc

19.9 Au, 19.4 g/t Ag

PLATSOLTM recovery
Au 96%, Ag 99.5%

No cyanide!

GALVANOX PROCESS
Process developed by David Dixon with Alain Tshilombo and Ghazaleh Nazari

35

GALVANOX FEATURES
Atmospheric Leach (~80C) No microbes Pure sulphate medium (no chloride) No fine grinding Generates elemental sulfur (> 95%), low oxygen demand No surfactants Selective for chalcopyrite over pyrite (can cost-effectively treat low grade concentrates down to 9% copper or less) Complete copper recovery, typically in less than 12 hours, and sometimes in as little as 4 hours Fully compatible with conventional SX-EW Conventional materials of construction

GALVANOX CHEMISTRY
GALVANOX takes advantage of the galvanic effect between chalcopyrite and pyrite.

Chalcopyrite is a semiconductor, and therefore corrodes electrochemically in oxidizing solutions.

In ferric sulphate media, the overall leaching reaction is as follows:

CuFeS2 + 2 Fe2(SO4)3 CuSO4 + 5 FeSO4 + 2 S0

This reaction may be represented as a combination of anodic and cathodic half-cell reactions:

Anodic: CuFeS2 Cu2+ + Fe2+ + 2 S0 + 4 e

Cathodic:4 Fe3+ + 4 e 4 Fe2+

UNASSISTED CHALCOPYRITE LEACHING

So Cu2+ 4 eFe2+ 4 Fe2+ 4 Fe3+

CuFeS2
Anodic Site Cathodic Site

UNASSISTED CHALCOPYRITE LEACHING

GALVANOX RATE CONTROL

Chalcopyrite appears passivated Anode passivation due to iron depleted sulphide Anode or cathode? Dixon and Tshilombo passivation appears to be at cathode (ferric reduction) Pyrite catalyzes the cathodic process in galvanic leaching Pyrite is inert and can be recycled

GALVANICALLY ASSISTED CHALCOPYRITE LEACHING

Py Cu2+

Cp 4 e4 e-

4 Fe3+

4 Fe2+ Fe2+ So
Anodic Site

Py

Cathodic Site

GALVANICALLY ASSISTED CHALCOPYRITE LEACHING

Partially leached particle

Completely leached particles

GALVANOX CHEMISTRY
The ferric required for GALVANOX leaching is regenerated in situ with oxygen gas

Ferric leaching of chalcopyrite:

CuFeS2 + 2 Fe2(SO4)3 CuSO4 + 5 FeSO4 + 2 S0 Oxidation of ferrous with dissolved oxygen gas: 4 FeSO4 + O2 + 2 H2SO4 2 Fe2(SO4)3 + 2 H2O Overall leaching reaction: CuFeS2 + O2 + 2 H2SO4 CuSO4 + FeSO4 + 2 S0 + 2 H2O Conventional SX-EW of Cu and Fe Precipitation

GALVANOX CHEMISTRY
In summary, the overall GALVANOX process chemistry is as follows:

Galvanically-assisted atmospheric leaching of chalcopyrite:

CuFeS2 + O2 + 2 H2SO4 Iron oxyhydrolysis: CuSO4 + FeSO4 + 2 S0 + 2 H2O

FeSO4 + O2 + H2O
Copper electrowinning: CuSO4 + H2O CuFeS2 +
5/ 4

Fe2O3 (s) + H2SO4

Cu0 + O2 + H2SO4

Overall process chemistry:

O2 Cu0 + 2 S0 + O2 + Fe2O3 (s)

BATCH TESTING
Six 3-L jacketed reactors

Water baths for temperature control

Digital oxygen mass flow meters for potential control Automated data acquisition for potential, pH and temperature

CHALCOPYRITE CONCENTRATE #1 35% Cu Effect of pyrite addition (50 g con, 65 g acid, 470 mV, 80 C)
100% 90% 80% 70%

Cu Recovery

60% 50% 40% 30% 20% 10% 0% 0 4 8 12 16 20 24 Py = 150 g (K5) Py = 100 g (K9) Py = 50 g (K6) Py = 25 g (K10) Py = 0 g (K1)

Time (h)

CHALCOPYRITE CONCENTRATE #2 23.6 % Cu Effect of pyrite addn (30 g con, 120 g Py, 30 g acid, 480 mV, 80 C)
100% 90% 80% 70%

Cu Recovery

60% 50% 40% 30% 20% 10% 0% 0 4 8 12 16 20 24 Galvanox Leaching No Pyrite

Time (h)

CHALCOPYRITE CONCENTRATE #3 24.1 % Cu Effect of pyrite addn (10 g con, 40 g Py, 15 g acid, 470 mV, 80 C)
100% 90% 80% 70%

Cu Recovery

60% 50% 40% 30% 20% 10% 0% 0 4 8 12 16 20 24 Galvanox Leaching No Pyrite

Time (h)

CHALCOPYRITE CONCENTRATE #4 20.1 % Cu Effect of pyrite addn (57 g con, 112 g Py, 60 g acid, 450 mV, 80 C)
100% 90% 80% 70%

Cu Recovery

60% 50% 40% 30% 20% 10% 0% 0 4 8 12 16 20 24 Galvanox Leaching No Pyrite

Time (h)

CHALCOPYRITE BULK CONCENTRATE 10.2% Cu (150 g bulk con @ ~1.21 Py/Cp ratio, 75 g acid, 440 mV, 80 C)
100% 90% 80% 70%

Cu Recovery

60% 50% 40% 30% 20% 10% 0% 0 4 8 12 16 20 24

Time (h)

KEY QUESTIONS
ARE ALL PYRITES EQUAL? (NO!) CAN PYRITE BE IMPROVED IN CATALYTIC ABILITY? (YES WITH A SILVER SURFACE TREATMENT) HOW DO YOU HAVE GALVANIC CONTACT WHEN THE CHALCOPYRITE GETS COATED IN ELEMENTAL SULPHUR (A NATURAL INSULATOR? (INTERESTING ANSWER!) WHAT ABOUT OTHER REFRACTORY COPPER SULPHIDES? (GALVANOX HAS BEEN ADAPTED TO TREATMENT OF ENARGITE)

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Experiments (Ghazaleh Nazari Ph.D.)

Investigating the effect of various parameters on the kinetics of chalcopyrite leaching:
Mass ratio of silver-enhanced Py/Cp Silver concentration on pyrite

Solution potential
Pyrite recycle Pulp density

Comparison of silver-catalyzed leaching and silverenhanced pyrite-catalyzed leaching

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Unassisted chalcopyrite leaching

100% 80%

Copper Extraction

60%

40%

20%

0% 0 10 20 30 40 50 Time (h) 60 70 80 90

Potential set point = 470 mV (vs. Ag/AgCl), T = 80C

53

Silver-enhanced pyrite addition Comparison Natural pyrite addition

100% 100% 100% 80% 80% 80%

Extraction Copper Copper Extraction Copper Extraction

60% 60% 60% 40% 40% 40%

Pyrite #3, Py/CpPy = 6, #1 Ag/Py = 100 ppm

20% 20% 20% 0% 0% 0 0% 0 0
Py #2 #3 Pyrite #1,Py/Cp Py = 6, Ag/Py = 100 ppm Pyrite #1, Py/Cp =6 Py #3, Ag/Py = 100 ppm Py #1, Ag/Py = 100 ppm Pyrite #2, Py/Cp =6 Pyrite #2,Py/Cp Py = 6, Ag/Py ppm #2, Ag/Py= =100 100 ppm

20 2 20

40 60 4 6 Time (h) 40 Time (h) 60 Time (h)

Pyrite #3, Py/Cp = 6 80 100 8 10 80 100

Potential set point = 470 mV (vs. Ag/AgCl), T = 80C

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Recycled pyrite at low pulp density at different solution potentials

100%

100%

80%

80%

Copper Extraction

Copper Extraction

60%

60%

40%

40%

20%

0% 0 10 20

Py/Cp = 4, Ag/Py = 100 ppm, E = 450 mV Py/Cp = 4, Ag/Py = 100 ppm, E = 440 mV Py/Cp = 4, Ag/Py = 100 ppm, E = 470 mV Py/Cp = 4, Ag/Py = 100 ppm, E = 420 mV 30 Time (h) 40 50 60

20%

0% 0 10

Py/Cp = 4, Ag/Py = 100 ppm, E = 450 mV, Py Recycle Py/Cp = 4, Ag/Py = 100 ppm, E = 440 mV, Py Recycle Py/Cp = 4, Ag/Py = 100 ppm, E = 470 mV, Py Recycle Py/Cp = 4, Ag/Py = 100 ppm, E = 420 mV, Py Recycle 20 30 Time (h) 40 50 60

Fresh pyrite

Recycled pyrite

10 g/L Cu concentrate, T = 80C

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High pulp density

100% 80%

Copper Extraction

60%

40%

20%
Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, 2nd Py Recycle Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, Fresh Py Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, 1st Py Recycle

0% 0 2

4 Time (h)

10

70 g/L Cu concentrate, T = 80C

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Silver Catalyzed Leaching

The copper extraction from chalcopyrite increases in ferric sulfate solution by addition of silver as a soluble silver salt.

Formation of an intermediate Ag2S film

CuFeS2 + 4 Ag+ 2 Ag2S (chalcopyrite surface) + Cu2+ + Fe2+ Ag2S + 2 Fe3+ 2 Ag+ + 2 Fe2+ + S0

57

Silver-Catalyzed Leaching
Silver availability Silver availability is affected by the formation of argentojarosite during leaching: 3Fe2(SO4)3 + Ag2SO4 + 12H2O 2AgFe3(SO4)2(OH)6 + 6H2SO4 Silver toxicity (in biological leaching) Accumulation of silver sulfide on ferrooxidant cells has been observed Silver ions are toxic to most microorganisms Biooxidant growth is inhibited in the presence of even miniscule amounts of silver (as low as 0.1 ppm)

58

Comparison of silver-catalyzed leaching and enhanced pyritecatalyzed leaching

100%
100%

80%

80%
Copper Extraction

Copper Extraction

60%

60%

40%

40%

20% Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV Same Silver Added, No Pyrite Added, E = 450 mV 0% 0 20 40 Time (h) 60 80 100

20% Py/Cp = 2, Ag/Py = 100 ppm, E = 450 mV, Py Recycle Same Silver Added, No Pyrite Added, E = 450 mV 0% 0 20 40 Time (h) 60 80 100

Fresh pyrite

Recycled pyrite

0.61 g Ag/kg Cu, E = 450 mV, T = 80C

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Galvanically-Assisted Leaching
Chalcopyrite Cu2+ Pyrite Fe3+

CuFeS2 S0

e-

FeS2 Fe2+

Fe2+

Schematic diagram of galvanically-assisted chalcopyrite leaching

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Resistivity of sulfur product layer

Sample ID Sulfur with silver Sulfur without silver Resistivity 1.06 0.10 107 cm 8.05 0.15 1010 cm

Based on Ohms law and Faradays law and knowing the driving force Maximum Resistivity: 1.11 107 cm
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Sulfur Resistivity
14 13 12 11
Log () (.cm)

10 9 8 7 6 5 4 0 100 200 300 400 500 600 700 800 900 1000 Silver to Sulfur Ratio (ppm)

62

Enhanced pyrite with Ag and Hg

100%

80%

Copper Extraction

60%

40%

20%

Pyrite pretreated with silver, Ag/Py = 100 ppm Pyrite pretreated with mercury, Hg/Py = 600 ppm Natural pyrite, No Ag added, No Hg added
0% 0 20 40 60 80 Time (h) 100 120 140 160

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GALVANOX Conclusions
An improvement to the Galvanox process has been developed. As little as 60 mg of silver per kg of copper is sufficient to ensure complete copper extraction typically within 10 to 15 hours of leaching

The acceleration of chalcopyrite leaching in this process is attributed to the galvanic interaction between pyrite and chalcopyrite
Pyrite has a critical role in this process and it provides an additional surface for ferric reduction Silver has a critical role in this process: It decreases the resistivity of sulfur layer by the formation of dispersed silver sulfide particles It increases the catalytic properties of pyrite and the rate of ferric reduction increases on silver-enhanced pyrite

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WHAT OF THE FUTURE?