Corby Anderson

The Effective Hydrometallurgical Treatment of Arsenic Bearing Copper Ores and Concentrates
Eur Ing Dr. Corby G. Anderson QP CEng FIMMM FIChemE Harrison Western Professor Kroll Institute for Extractive Metallurgy Colorado School of Mines Golden, Colorado USA 80401
CORNISH MAN ENGINE MOUNTAIN MINE CIRCA 1850 Allihies, Beara Peninsula, Cork, Ireland
PERUMIN 30th Convencion Minera
ANCESTORS - ANACONDA SMELTER
The Stack was built by the Alphons Custodis Chimney Construction Company of New York. At the time it was built, May 5, 1919 it was the tallest masonry structure of any kind in the world at 585 feet.
Butte, Montana, USA Granite Mountain Fire Memorial June 8, 1917 168 Men Died
Dr. Corby G. Anderson
Big Creek, Idaho, USA

Sunshine Fire - May 2, 1972 - 91 Men Died
Colorado School of Mines

Est. 1874 Golden, Colorado 21 majors 193 Faculty 4300 students have a unique mission in energy, mineral, and materials science and engineering
Department of Metallurgical & Materials Engineering - MME

20 full time faculty members 5 Centers and Institutes: Kroll Institute for Extractive Metallurgy
Colorado Center for Advanced Ceramics Advanced Steel Processing & Products Res. Ctr. Center for Welding, Joining & Coating Research Advanced Coatings & Surface Engineering Res. Ctr.
Degrees:
PhD, MS, ME & BS in Metallurgical & Materials Engineering PhD & MS in Materials Science PhD & MS in Nuclear Engineering
Students:
Graduate level: 120 Undergraduate level: 50 per year
KIEM - Kroll Institute for Extractive Metallurgy & CR 3 - Center for Resource Recovery & Recycling
Patrick R. Taylor
Director, KIEM G.S. Ansell Distinguished Professor of Chemical Metallurgy EXPERTISE Mineral Processing Extractive Metallurgy Recycling Waste Treatment & Minimization Thermal Plasma Processing of Materials Thermal Plasma Processing of Wastes
Gerard P. Martins
Professor of Metallurgical and Materials Engineering
Brajendra Mishra
Director, CR3 Associate Director KIEM, Professor of Metallurgical and Materials Engineering EXPERTISE Pyrometallurgy Electrochemistry Materials synthesis Waste Processing Recycling Molten Salt Processing Oxidation Reactive & radioactive metals Glove box processing
Corby G. Anderson
Harrison Western Professor of Metallurgical and Materials Engineering
D. Erik Spiller
Research Professor of Metallurgical and Materials Engineering EXPERTISE
Paul B. Queneau
Research Professor of Metallurgical and Materials Engineering EXPERTISE
EXPERTISE EXPERTISE Process and extraction metallurgy Engineered ceramic and metal powders Electrochemical systems Corrosion Transport phenomena Reactor Design & kinetics Extractive Metallurgy Mineral Processing Recycling Waste Treatment & Minimization Mineral Processing Comminution Physical separation Recycling Flotation Leaching Liquid-solid separation Project management
Extractive and process metallurgy Pyrometallurgy Recycling Waste treatment and minimization
KIEM
The Kroll Institute for Extractive Metallurgy - KIEM Department of Metallurgical and Materials Engineering Colorado School of Mines www.mines.edu
ARSENIC
ARSENIC Name: Arsenic Symbol: As Atomic Number: 33 Atomic Mass: 74.9216 amu Melting Point: 817.0 C (1090.15 K, 1502.6 F) Boiling Point: 613.0 C (886.15 K, 1135.4 F) Number of Protons/Electrons: 33 Number of Neutrons: 42 Classification: Metalloid Crystal Structure: Rhombohedral Density @ 293 K: 5.72 g/cm3 Color: Gray
ARSENIC
ARSENIC
MERCURY
MERCURY Name: Mercury Symbol: Hg Atomic Number: 80 Atomic Mass: 200.59 amu Melting Point: -38.87 C (234.28 K, -37.966 F) Boiling Point: 356.58 C (629.73 K, 673.844 F) Number of Protons/Electrons: 80 Number of Neutrons: 121 Classification: Transition Metal Crystal Structure: Rhombohedral Density @ 293 K: 13.456 g/cm3 Color: Silver
MERCURY
MERCURY Aktashite Cu6Hg3As4S12 Cinnabar HgS Clearcreekite Hg (CO3)(OH) 2H2O CorderoiteHg3S2(Cl,Br)2 Kadyrelite Hg H(Br,Cl)3O2 Livingstonite HgSb4S8 Moschellandsbergite Ag2Hg3 Mosesite Hg2N(Cl,SO4,MoO4,CO3)(H2O) Myrickite Cinnibar in Quartz RouthieriteTl(Cu,Ag)(Hg,Zn)2(As,Sb)2S6 Terlinguaite Hg2OCl Tiemannite HgSe
Montroydite HgO Calomel HgCl

ANTIMONY
ANTIMONY
Name: Antimony Symbol: Sb Atomic Number: 51 Atomic Mass: 121.76 amu Melting Point: 630.0 C (903.15 K, 1166.0 F) Boiling Point: 1750.0 C (2023.15 K, 3182.0 F) Number of Protons/Electrons: 51 Number of Neutrons: 71 Classification: Metalloid Crystal Structure: Rhombohedral Density @ 293 K: 6.684 g/cm3 Color: bluish
ANTIMONY
ANTIMONY
Technical Routes of Treatment

Pressure Oxidation Roasting Selective Leaching of Impurities

Pressure Oxidation Advantage: Proven technology. Disadvantage: High costs and complex plant design and operation.

Roasting Advantage: Proven technology. Disadvantage: Challenges in containment and fixation of impurities.

Selective Leaching of Impurities Advantage: proven technology with moderate costs and control and fixation of contaminants. Disadvantage: Established technology but not well known.
ANDERSON ENARGITE PROJECTS

Marca Punta - Peru El Galeno - Peru Caspiche Chile Chelopech - Bulgaria Lepanto Phillipines Tampaken Phillipines Frieda River - New Guinea Golpu New Guineau Mt. Carlton Australia El Indio - Chile
Hydrometallurgical Processing of Gold Bearing Copper Enargite Concentrates

Dr. Corby G. Anderson Dr. Larry G. Twidwell
Alkaline Sulfide Leaching Copper Concentrate Industrial Plants
ASL
- Sunshine Mining 1945 2002
1st and Longest Operating Copper Concentrate Alkaline Sulfide Leach Plant. Produced Sb metal and removed Hg and As providing clean Cu smelter concentrate.
Nitrogen Species Catalyzed Leaching Copper Concentrate Industrial Plants
NSC - Sunshine Mining 1984 1995 1st and Longest Operating Copper Concentrate Pressure Leach Plant. Produced Ag and Cu.
Nitrogen Species Catalyzed Leaching Copper Concentrate Industrial Plants
Sunshine Mining 1984 1995 1st and Longest Operating Copper Concentrate Pressure Leach Plant.
Industrial Copper Pressure Leach History
Anaconda Arbiter Process 1974 Sunshine Mining Mt. Gordon Phelps Dodge Oxiana Kansanshi
1984 1998 2003 2005 2005
Nitrogen Species Catalyzed Metallurgical Uses

Dissolution of Yellow Cake Dissolution of Spent Uranium Fuel Elements Pickling Agent for Stainless Steel Uranium Concentrate Leaching Leaching of Phosphate Rock 1st Proposed 1909 for Metal Sulfide Oxidation
Nitrogen Species Catalyzed Leaching Fundamentals
3 MeS (S)+ 2HNO3 (Aq)+ 3H2SO4 (Aq) 3 MeSO4 + 3So (S) + 2NO (G) + 4H2O NaNO2
(Aq)
+ H+
HNO2 (Aq) + Na+ NO+ (Aq) + H2O 2Me+2 (Aq) + 2So + 4NO (G)
HNO2 (Aq) + H+ 2MeS (S) + 4NO+ (Aq)

Relative Potentials of Hydrometallurgical Oxidizers. E0hOxidant (pH = 0, H2 ref.) Fe+2 0.770 V NO(g) + 2H2O 0.957 V NO(g) + H2O 2H2O 2 ClNO(g) 1.202 V 1.230 V 1.358 V 1.450 V
Redox Fe+3 HNO3 HNO2 O2 (g) Cl2 (g) NO+
Equation Fe+3 + e-
NO3- + 4H+ +3eNO2 - + 2H+ + eO2 + 4H+ + 4eCl2 (g) + 2e NO+ + e-
2NO (G) + O2 (G) < --> 2NO2 (G) 2NO2 (G) <--> 2NO2 (Aq) 2NO2 (Aq) + 2NO (Aq) + 4H+ <--> 4NO+ (Aq) + 2H2O
2MeS (G) + 4H+ + O2 (G)
2Me+2 (Aq) + 2So + 2H2O
NSC Process Advantages

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. First and Only Long Term Industrial Pressure Leach Process for Copper Concentrates Faster Reaction Rate Smaller Reaction Autoclave Volume Required Eh/ORP Very High No Exotic/Expensive Materials of Construction No Titanium Needed No Fire Danger No Oxygen Dip Tube Low Autoclave Temperatures (125oC or170oC) Low Pressures (620 kPag or 975 kPag) kPag)
NSC Process Advantages

11. 12. 13. 14. 15. 16. 17. 18. 19. No Brick or Lead Autoclave Liners Less and Simpler Autoclave Maintenance No Special Agitator System for O2 Mass Transfer to Solution Easier Feed Pump, Choke and Flash System Design and Operation along with Direct Heat Exchange/Recovery Like Smelting, Au and Ag Recovery is Excellent No Complex Chloride Chemistry or Corrosion to Deal with. No Major Economic or Environmental Issues Because of Limited Nitrogen Species Use in Process Lower Capital and Operating Costs Simple, Industrially Proven By-Product Sulfur Handling ByResults in Value Added Products or Regenerated Reagents.
Nitrogen Species Catalyzed Current Applications

- Copper Enargite Concentrates : South America
Molybdenum Disulfide/Rhenium Concentrates : United States Gold Pyrite Concentrates : China Gold Arsenopyrite Concentrates : Asia Gold Pyritic Tailings : South America Silver Bearing Concentrates and Pyritic Ores : South America - Copper, Zinc, Nickel, Cobalt PMs Australia - Cobalt, Copper, Gold United States Detailed Design Underway
Partial Nitrogen Species Catalyzed Oxidation of a Copper Enargite Concentrate

Composition of Enargite Concentrate Tested Cu, % 19.7 Fe, % As, % Au, g/T Tot. S. % p80 % 24.3 5.4 4.3 34.3 25 micron
STAT EASE
This commercially licensed program based on fundamentals of design of experimentation provides highly efficient: Two-level factorial screening studies so that the vital factors which affect a process can be identified. Response surface methods to find ideal process settings and achieve optimal performance. Mixture design techniques to discover optimal outcomes.
STAT EASE
The Google product of applied testing and optimization. Industrial laboratory testing and optimization clients want; Maximum results Short turnaround Low cost Usually they have minimal amounts of representative samples.
DOE NSC MATRIX

TABLE 1. STAT EASE DESIGN EXPERT TEST MATRIX. Std Run Grind Time Initial Acid Max. Temp. Leach Time 1 1 0 min 50 g/L 150 C 120 min 7 2 0 min 100 g/L 130 C 60 min 5 3 0 min 50 g/L 150 C 60 min 10 4 5 min 75 g/L 140 C 90 min 3 5 0 min 100 g/L 130 C 120 min 4 6 10 min 100 g/L 150 C 60 min 6 7 10 min 50 g/L 130 C 120 min 2 8 10 min 50 g/L 130 C 60 min 8 9 10 min 100 g/L 150 C 120 min 9 10 5 min 75 g/L 140 C 90 min
NSC TEST CONDITIONS

TABLE 2. NSC ENARGITE PARTIAL OXIDATION Nitrogen Species Catalyzed Partial Oxidation Leach Conditions. Grind Time = Table 1 Initial Free Sulfuric Acid = Table 1 Reactor Working Pressure = 620 kPag Slurry Solids Content = Table 1 Maximum Temperature = Table 1 Total Time = Table 1 Nitrogen Species Concentration = 2.0 g/L
NSC DOE TEST RESULTS

TABLE 3. NSC TESTING RESULTS Std 1 7 5 10 3 4 6 2 8 9 Run As Rec. 1 38.21 % 2 18.34 % 3 27.75 % 4 48.44 % 5 11.38 % 6 29.73 % 7 65.63 % 8 58.99 % 9 53.30 % 10 48.44 % Cu Rec 38.96 % 26.56 % 30.03 % 53.81 % 19.18 % 74.39 % 68.80 % 86.92 % 55.97 % 53.81 % Fe, Rec 80.57 % 84.15 % 80.34 % 78.55 % 58.29 % 1.07 % 69.92 % 32.17 % 65.92 % 78.55 %
NSC STAT EASE MODEL

Final Copper Equation in Terms of Actual Factors
Cu Recovery = +62.98042 +4.2837 * Grind Time -0.12732 * Solids -0.28707 * Initial Acidity -0.026375 * Temperature +0.061833 * Leach Time +2.13467E-003 * Solids * Initial Acidity -2.76833E-003 * Solids * Leach Time Std. Dev. Mean 50.84 0.000 R-Squared Adj R-Squared 1.00 1.00
NSC STAT EASE RESPONSE

DESIGN- EXPERT Plot Cu Recover y Design Points X = B: Solids Y = C: Ini tial Acidity Actual Factor s A: Gr ind Time = 10.0 D: Temper atur e = 130.0 E: Leach Time = 60.0
100.0
Cu Recovery
81.3
72.8
CI i i lAi i y : nt a cdt
62.5
76.0
43.8
81.0
25.0 50.0 62.5 75.0 87.5 100.0
B: Solids

DESIGN- EXPERT Plot As Recover y X = B: Solids Y = C: Initial Acidity Actual Factor s A: Gr ind Time = 10.0 D: Temper atur e = 140.0 E: Leach Time = 60.0
100.0
As Recovery
81.3
C In ia A id y : it l c it
51.0 48.7
62.5
55.0
43.9
39.3
43.8
34.6
25.0 50.0 62.5 75.0 87.5 100.0
B: S olids

100
S Oxidized, %
33.1
32.0
Initial Acidity, g/L
81
63
30.0
32.0 28.0
44
26.0 24.0
25 50 63 75 Solids, g/L 88 100
Influence of initial acidity and solids content on sulfur oxidized (Constants: Grind Time, 10 min; T 130 C; Leach Time, 60 min)

100
Acid Generation, g/g concentrate

0.60
81
0.40
Initial Acidity, g/L
0.30
0.20
63
0.10
44
0.05
25 50 63 75 Solids, g/L 88 100
Influence of initial acidity and solids content on acid generation (Constants: Grind Time, 10 min; T 130 C; Leach Time, 60 min)
OPTIMIZED NSC PARTIAL OXIDATION

Nitrogen Species Catalyzed Partial Oxidation Leach Conditions. Grind Time = 25 minutes Initial Free Sulfuric Acid = 25 g/L Reactor Working Pressure = 620 kPag Slurry Solids Content = 50 g/L Maximum Temperature = 130 C Total Time = 60 minutes Nitrogen Species Concentration = 2.0 g/L Copper Recovery = 95.01 % Iron Recovery = 78.46 % Arsenic Recovery = 86.93 % Acid Generation = 0.125 g/g Concentrate % Sulfur Oxidized to Solution = 67.11
OPTIMIZED LOCKED CYCLE NSC PARTIAL OXIDATION

Leaching Cycles = 8 Grind Time = 40 minutes Initial Free Sulfuric Acid = 25 g/L Reactor Working Pressure = 620 kPag Slurry Solids Content = 50 g/L Maximum Temperature = 130 C Total Leach Tine = 45 minutes Nitrogen Species Concentration = 2.0 g/L Particle Size = 80% passing 15 micron Copper Recovery = 97.8 % Iron Recovery = 51.2 % Arsenic Recovery = 72.1 % Mass Reduction = 64.91 % Acid Generation = 0.06 g/g Concentrate % Sulfur Oxidized to Solution = 62.66 % Oxygen Consumption = 0.891 g/g concentrate
ARSENIC REMOVAL AND FIXATION

Three methods for removing arsenic from solution were investigated: Elevated Ambient Temperature Formation of Scorodite Autoclave Formation of Scorodite Ambient Temperature (25 C) Removal of Arsenic by Ferrihydrite Formation and Adsorption
Scorodite was produced to be used as seed for subsequent experiments by precipitation from one-liter of 0.3 M Ferric Nitrate, 25 g/L As(V) solution at 160 C, 24 hours.
Autoclave Formation of Scorodite

Autoclave leach solution-1 was pH adjusted to 1.06 and subjected to autoclave precipitation. The experimental test conditions were: 1-liter of solution was placed in the autoclave. 20-g/L of scorodite seed was added, the temperature was raised to 160 C, held for 5-hr. The results are presented in the next slide This approach was successful and may be a viable option, i.e. the arsenic is effectively removed as scorodite, yet little copper is lost to the solids.

Solution pH Removed from Solution,% (final conc, mg/L) As Cu 1.06 Head 0 (1760) 0 (7262) 1.11 97.9 (36.5) 1.9 (7127)
Final phase formed confirmed by XRD is scorodite.
Ambient Temperature (25 C) Removal of Arsenic by Ferrihydrite Formation and Adsorption

Solution pH As Concentration, mg/L Fe Cu
0.7 (head) 3.1 4.0 4.5 4.6 5.0
2774.0 105.94 6.78 <0.03 DL <0.03 DL <0.03 DL
11720.0 823.7 139.5 52.0 48.4 44.0
8352.0 8681.4 8151.2 5221.7 4396.4 2568.3
Ambient Temperature (25 C) Removal of Arsenic by Ferrihydrite Formation and Adsorption

Removal by Ferrihydrite Adsorption
12000 10000 8000 [M], mg/L As 6000 4000 2000 0 0 1 2 pH 3 4 5 Fe Cu
NSC Partial Oxidation Enargite Flowsheet

Split Thickener Overflow A Enargite Concentrate H2SO4 NaNO2 O2
Sp lit Th icken er O verflo w B
MIXING TANK BALL MILL
THICKENER AUTOCLAVE Solids to ASL Gold Recovery
Copper Solution FILTER PRESS
ELECTROWINNING CELL Copper Metal Ferrihydrite Precipitation FILTER PRESS Copper Cement
MIXER SETTLER TANK Raffinate
FILTER PRESS AUTOCLAVE (for Scorodite) Solids to ASL Gold Recovery
Scorodite Iron Metal
CEMENTATION TANK
Partial Nitrogen Species Catalyzed Pressure Oxidation of a Cobaltite Chalcopyrite Concentrate

It is now proposed that the NSC pressure leach facility be used to treat a gold bearing chalcopyrite and cobaltite concentrate. NSC concentrate leach testing has been conducted at and the results were as follows. Table 35. Composition of Concentrate Tested.
Cu, % Co, % 7.2 14.4
Fe, % 14.4
As, % 20.0
Au, o/T 0.42
Total S, % 19.0
Nitrogen Species Catalyzed Partial Oxidation Leach Conditions.

Operating Criteria Initial Free Sulphuric Acid Reactor Working Pressure Slurry Solids Content Solids Size Maximum Temperature Nitrogen Species Concentration Reaction Time Unit 100 g/L 620 kPag 100 g/L 80% -10 micron 125C 2.0 g/L 20 min
Mass Distribution of Nitrogen Species Catalyzed Pressure Leaching of Cobaltite, Chalcopyrite Gold Concentrate. As seen the copper, cobalt and arsenic are solubilized and can be separated by conventional means with the sulphide oxidized to sulphur in a minimum amount of time.The gold is concentrated in the solids for recovery by alkaline sulphide leaching solids. Cu, % Solution 97.3 Solid 2.7 Co, % 97.7 2.3 Fe, % 97.7 2.3 As % 93.4 6.6 Au, % 0.0 100.0
Alkaline Sulfide Hydrometallurgy Fundamentals

Very selective lixiviant. Only As, Hg, Sb, Au and Sn have significant solubilities. Used industrially for Sb production in, USA, USSR and China. Piloted for Sb and Au in Australia
Alkaline Sulfide Hydrometallurgy Current Applications

-- Antimony and PM : Australia and Europe
Gold Pyrite Concentrates : China Gold Arsenopyrite Concentrates : Asia Gold Pyritic Tailings : South America Copper Enargite : South America - Copper Enargite : Asia/South Africa - Copper Enargite : Asia./Australia
Alkaline Sulfide Hydrometallurgy Alkaline Sulfide Hydrometallurgy - Sulfur Stability Diagram. Fundamentals

4S + 6OH- 2S2- + S2O32- + H2O (X-1)S + S2- S2-X (where X = 2 to 5) SX2- + 2(X-1)e- xS2S22- + 2e- 2S2-
Alkaline Sulfide Hydrometallurgy - Sulfur Meta Stable Diagram.

Alkaline Sulfide Solutions Alkaline Sulfide Hydrometallurgy Fundamentals

Na2S + As2S3 NaAsS2 + Na2S 2NaAsS2 Na3AsS3 NaAsS2 + 3 NaOH
1.5 H2O + 2 Na2S + As2O3 NaAsS2 + Na2S Na3AsS3

Na3AsS4 + 2 O2 Na3AsO4 2 O2 + Na2S Na2SO4 3.5 O2 + 2NaOH + Na2S2 2Na2SO4 + H2O 8 O2 + 8NaOH + Na2S5 5Na2SO4 + 4H2O 2NaOH + 2 O2 + Na2S2O3 2Na2SO4 + H2O Arsenic is then precipitated by iron salt addition.
Alkaline Sulfide Waste Solution Treatment

~ 100% sulfide oxidation to sulfate Sodium sulfate crystals were precipitated from the treated solution XRD scans confirmed Na2SO4

Sodium Sulfate (Na2SO4) and Gypsum (CaSO4) As a Value Added By-product or for Sodium Hydroxide Regeneration Sodium Sulfate Pulp and Paper Manufacture, Glass Industry, Ceramic Industry, Detergents, Feed Supplements, Textile Dyes, Bleaching, Photography Gypsum Soil Amendment for Agriculture or Cement Manufacture Key Reagent Regenerations from Sodium Sulfate Sulfuric Acid and Caustic Required for Process Ammonium Sulfate Fertilizer can be Produced

Sodium Sulfate Production
2O2 + Na2S Na2SO4 3.5O2 + 2NaOH + Na2S2 2Na2SO4 + H2O 8O2 + 8NaOH + Na2S5 5Na2SO4 + 4H2O 2NaOH + 2O2 + Na2S2O3 2Na2SO4 + H2O
Gypsum Production
Na2SO4 + Ca(OH)2 CaSO4 + NaOH
Key Reagent Regeneration Reactions from Sodium Sulfate

Na2SO4 + 2H2O Or 2NH4OH + Na2SO4 2NaOH + (NH4)2SO4 H2SO4 + 2NaOH
Laboratory Electrodialysis Cell.
Key Reagent Regeneration Reactions from Sodium Sulfate

Na2SO4 + 2H2O H2SO4 + 2NaOH
Gold lixiviation in the alkaline sulfide system postulated to be the result of oxidation by polysulfide and complexation as a sulfide . Leaching may occur as; Auo + S5-2 AuS5- + e-
Recovered by EW, cementation, chemical or gaseous precipitation, IX, SX.
PERUMIN EPD 2003, March 2-6 30th Convencion Minera
Alkaline Sulfide Gold Leaching Design of Experiments
Alkaline Sulfide Gold Recovery Adsorption

Alkaline Sulfide Gold Leach Head Solution Assay. Volume L Au 0.5 88.7 ppm Sb 21.0 g/L As Hg 5.31 g/L 274 ppm Sn 1.84 g/L

Alkaline Sulfide Gold Leach Head Final Assay. Volume L 0.5 Au 1.5 ppm Sb 21.1 g/L As 5.21 g/L Hg 274 ppm Sn 1.89 g/L

Overall Gold Selectivity and Recovery. Liquid 1.7% 100.0% 100.0% 100.0% 100.0% Solid 98.3% 0.0% 0.0% 0.0% 0.0%
Gold Antimony Arsenic Tin Mercury
Alkaline Sulfide Gold Recovery Electrowinning Cementation Gaseous Precipitation Chemical Precipitation Solvent Extraction Ion Exchange
Electrowinning of Alkaline Sulfide Leach Solution for Gold Recovery
Alkaline Sulfide Hydrometallurgy Application

ANALYSIS OF ENARGITE CONCENTRATE Table 1. Concentrate Analysis. Cu, % Fe, % As, % Au, o/T SiO2, % Ca, % Al, % 15.83 16.59 0.87 0.10 20.11 1.21 3.56 X-ray diffraction analysis and MLA was undertaken to characterize the concentrate. The major phases present are Enargite, Cu3AsS4 and Quartz, SiO2.
Alkaline Sulfide Hydrometallurgy Enargite Application

Alkaline Sulfide Leaching Conditions. Slurry Solids Content = 400 g/L Maximum Temperature = 103o C NaOH Concentration = 25.0 g/L S-2 Concentration = 60.0 g/L Total Time = 12 Hours

Alkaline Sulfide Timed As Recoveries. Time, Hr 0 1 2 4 6 12 % As Leached 0.0 64.3 84.3 91.2 91.6 91.6

Mass Distribution of Alkaline Sulfide Leach Products Cu , % As , % Au, % Solution 0.0 91.6 32.6 Residue 100.0 8.4 67.4 Mass Reduction = 0.41 %
As, Au and Cu Leaching 400 g/L Solids, 103 C & 6 Hours.

100.0 90.0 80.0 70.0 60.0 Percent 50.0 40.0 30.0 20.0 10.0 0.0 10.0
20.0
30.0
40.0 S-2 Concentration (g/L)
50.0
60.0
70.0
SOLUTION Cu%
SOLUTION As%
SOLUTION Au%
RESIDUE Cu%
RESIDUE As%
RESIDUE Au%

Locked Cycle Leaching Results Slurry Solids = 400 g/L Leach Temperature = 100O C NaOH = 25.0 g/L S-2 = 60.0 g/L Reaction Time = 4.0 Hrs Locked Test Cycles = 7 Final Concentrate Weight Gain = 8.05 % Reagent Consumption NaOH = 17.65 Kg/Dry Tonne Concentrate Na2S = 73.2 Kg/Tonne Dry Concentrate Copper Recovered to Liquid = 0.00 % Arsenic Recovered to Liquid = 93.72 % Antimony Recovered to Liquid = 50.15 % Silver Recovered to Liquid = 0.00 % Gold Recovered to Liquid = 22.98 %

Final Locked Cycle Leached Concentrate Analysis.
Cu, % Fe, % As, % Au, o/T SiO2, % Ca, % Al, % 16.54 16.61 0.01 0.07 20.11 1.21 3.56
ALKALINE SULFIDE ENARGITE FLOWSHEET

Enargite Concentrate
ASL Leaching
Liquid
Thickener
Solid
Recycle 95 %
Liquid Drum Filter
Filter Press
Liquid Drum Filter Solid Liquid
Solid
Solid Tank
Solids to Smelter
Autoclave Tails Treatment
Bleedstream 5 %
Iron Salts
Gold Recovery
Tank
THE INDUSTRIAL ALKALINE SULFIDE HYDROMETALLURGICAL TREATMENT OF MERCURY BEARING ANTIMONY ORES AND CONCENTRATES Corby G. Anderson
Mercury is commonly found in association with antimony ores.

Cinnabar, HgS Livingstonite, HgSb4S7 Tetrahedrite, Cu12Sb4S13 Stibnite, Sb2S3 Found in Algeria, Mexico, USSR, Slovakia, Tajikistan, China and North America.
The alkaline sulfide system is a very selective lixiviant for antimony, arsenic, tin, gold and mercury in lieu of other metals
.
Na2S + Sb2S3 NaSbS2 + Na2S
2NaSbS2 Na3SbS3
Na2S + HgS
+ Na2HgS2
Eh-pH Diagram for Mercury in the Alkaline Sulfide System.

2 HSO4- SO42Hg2+ 1 HgSO4(a) Hg2SO4 S 0 HgS Hg(l) HgO
Eh (v volts)
-1 Hg(l) H2S(a) -2 0 2 4 6 8 HS10
HgS22-
S212 14
pH
Na2S + SnS2 3Na2S + As2S3
+ Na2SnS3 2Na3AsS3
4So + 6NaOH (X-1) So + Na2S
2Na2S + Na2S2O3 + 3H2O Na2SX (where X= 2 to 5)
Gold lixiviation in the alkaline sulfide system postulated to be the result of oxidation by polysulfide and complexation as a sulfide . Leaching may occur as; Auo + S5-2 AuS5- + e-
Recovered by EW, cementation, chemical or gaseous precipitation, IX, SX.
Na2SX + (X-1)Na3SbS3
(X-1)Na3SbS4 + Na2S
Electrowinning of Antimony
The primary anode reactions are; 4OHS-2 The primary cathode reaction is; SbS3
-3
4e- + 2H2O + O2 2e- + SO
+ 3e-
SbO + 3S-2
Sodium Hydroxy Antimonate Production

2H2O + 2NaOH + Na3SbS4 + 4O2 2Na2HgS2 + H2O + O2 NaSb(OH)6 + 2Na2S2O3
2HgS + Na2S2O3 + 2NaOH
Applications to Antimony Ores

Slovakia Tajikistan Chile Peru Mexico North America Australia Sweden ????
Roznava Tetrahedrite Concentrate.

Sb, %, As, % Hg, %, Cu, %, Fe, % Ag, ppm Au, ppm TS, % 17.3 1.85 0.55 26.1 12.4 6,400 2.0 22.0
Alkaline Sulfide Leach Testing Conditions.

Leach Time = 12 Hr. Roznava Concentrate = 100 g/L Leach Temperature = 105O C Sulfur Addition = 20 g/L Sodium Hydroxide = 35 g/L Sb Leached = 95.0 % As Leached = 60.0 % Hg Leached =95.0 % Au Leached = 20.0 % Cu Leached = 0.0 % Ag Leached = 0.0 %
Roznava Concentrate After Alkaline Sulfide Leaching.

Sb, %, As, % Hg, %, Cu, %, Fe, % Ag, ppm Au, ppm TS, % 0.87 0.74 0.03 26.1 12.4 6,400 1.6 22.0
Proposed Slovakian Plant Technology.

Alkaline sulfide leaching. Solution purification by selective crystallization. Mercury removal along with waste antimonate production. Mercury selectively leached, stabilized, encapsulated and stored. Alkaline sulfide lixiviated gold recovered by IX.
Slovakian Alkaline Sulfide Hydrometallurgical Economics.

There was some existing infrastructure. Local costs for reagents, manpower and utilities were used. Mercury is separated, stabilized and locally stored. The plant produces 1,000 tons of high grade antimony per year by electrowinning from Roznava mercury bearing tetrahedrite concentrates. The capital costs include installed equipment, piping, instrumentation and engineering. Copper concentrates suitable for smelter treatment will be produced.

Estimated Unit Operating Costs.
Sulfur = $ 0.025 USD/lb EW Sb produced Caustic = $ 0.20 USD/lb EW Sb produced Steam = $ 0.20 USD/lb EW Sb produced Electricity = $ 0.20 USD/lb EW Sb produced Oxygen = $ 0.10 USD/lb EW Sb produced Waste treatment = $ 0.025 EW USD/lb Sb produced Wages = $ 0.10 USD/lb EW Sb produced Maintenance = $ 0.05 USD/lb EW Sb produced Total Operating Cost = $ 0.90 USD /lb EW Sb produced

Estimated Unit Capital Costs. Leaching and Solid Liquid Separation = Solution Purification = Electrowinning = Waste Treatment = First Fills and Working Capital = Total Capital Cost = $ 3,500,000.00 USD $ 1,500,000.00 USD $ 2,500,000.00 USD $ 1,000,000.00 USD $1,500,000.00 USD $ 10,000,000.00 USD
Alkaline Sulfide Recovery Of Gold Utilizing Nitrogen Species Catalyzed Pressure Leaching
Dr. Corby G. Anderson
Gold Concentrate Treated With Complete NSC Sulfide Oxidation Gold = 35 g/T Iron = 25.0% Arsenic = 6.31% Total Sulfur = 24.0% This Kazakh arsenopyrite concentrate also has high carbon leading to preg robbing.
Nitrogen Species Catalyzed Complete Sulfide Oxidation Leach Conditions. Initial Free Sulfuric Acid = 20 g/L Reactor Working Pressure = 975 kPag Slurry Solids Content = 100 g/L Solids Size = 80% minus 10 micron Maximum Temperature = 170o C Nitrogen Species Concentration = 2.0 g/L Reaction Time = 45 minutes
CIL Gold Recovery From Complete NSC Sulfide Oxidation. CIL Au recovery = 94.2%
Gold Concentrate Treated With Partial NSC Sulfide Oxidation Gold = 35 g/T Arsenic = 6.31% Iron = 25.0% Total Sulfur = 24.0%
Nitrogen Species Catalyzed Partial Sulfide Oxidation Leach Conditions. Initial Free Sulfuric Acid = 50 g/L Reactor Working Pressure = 620 kPag Slurry Solids Content = 100 g/L Solids Size = 80% minus 10 micron Maximum Temperature = 125o C Nitrogen Species Concentration = 2.0 g/L Reaction Time = 30 minutes
Alkaline Sulfide Recovery With Partial NSC Sulfide Oxidation. Alkaline Sulfide Au recovery = 93.3% No cyanide is used to avoid preg robbing !!
Conclusion Hydrometallurgy is very effective in the treatment of complex copper concentrates which contain impurities such as arsenic, antimony and mercury.
Thank you for this opportunity ! I look forward to my next visit to Peru.
The Effective Hydrometallurgical Treatment of Arsenic Bearing Copper Ores and Concentrates
Eur Ing Dr. Corby G. Anderson QP CEng FIMMM FIChemE Harrison Western Professor Kroll Institute for Extractive Metallurgy Colorado School of Mines Golden, Colorado USA 80401

Corby Anderson

Caricato da

Informazioni sul documento

Descrizione originale:

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Corby Anderson

Caricato da

Copyright:

Formati disponibili

The Effective Hydrometallurgical Treatment of Arsenic Bearing Copper Ores and Concentrates

PERUMIN 30th Convencion Minera

ANCESTORS - ANACONDA SMELTER

PERUMIN 30th Convencion Minera

Big Creek, Idaho, USA

PERUMIN 30th Convencion Minera

Colorado School of Mines

Department of Metallurgical & Materials Engineering - MME

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

Montroydite HgO Calomel HgCl

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

Technical Routes of Treatment

PERUMIN 30th Convencion Minera

Technical Routes of Treatment

PERUMIN 30th Convencion Minera

Technical Routes of Treatment

PERUMIN 30th Convencion Minera

Technical Routes of Treatment

PERUMIN 30th Convencion Minera

ANDERSON ENARGITE PROJECTS

PERUMIN 30th Convencion Minera

Hydrometallurgical Processing of Gold Bearing Copper Enargite Concentrates

PERUMIN 30th Convencion Minera

Alkaline Sulfide Leaching Copper Concentrate Industrial Plants

- Sunshine Mining 1945 2002

Nitrogen Species Catalyzed Leaching Copper Concentrate Industrial Plants

Nitrogen Species Catalyzed Leaching Copper Concentrate Industrial Plants

PERUMIN 30th Convencion Minera

Industrial Copper Pressure Leach History

1984 1998 2003 2005 2005

Nitrogen Species Catalyzed Metallurgical Uses

PERUMIN 30th Convencion Minera

Nitrogen Species Catalyzed Leaching Fundamentals

HNO2 (Aq) + H+ 2MeS (S) + 4NO+ (Aq)

PERUMIN 30th Convencion Minera

Nitrogen Species Catalyzed Leaching Fundamentals

Redox Fe+3 HNO3 HNO2 O2 (g) Cl2 (g) NO+

NO3- + 4H+ +3eNO2 - + 2H+ + eO2 + 4H+ + 4eCl2 (g) + 2e NO+ + e-

PERUMIN 30th Convencion Minera

Nitrogen Species Catalyzed Leaching Fundamentals

PERUMIN 30th Convencion Minera

Nitrogen Species Catalyzed Leaching Fundamentals

2MeS (G) + 4H+ + O2 (G)

2Me+2 (Aq) + 2So + 2H2O

PERUMIN 30th Convencion Minera

NSC Process Advantages

PERUMIN 30th Convencion Minera

NSC Process Advantages

PERUMIN 30th Convencion Minera

Nitrogen Species Catalyzed Current Applications

Partial Nitrogen Species Catalyzed Oxidation of a Copper Enargite Concentrate

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera

PERUMIN 30th Convencion Minera