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Lead- Zinc 2023
Changsha, China
October 20230
Hydrometallurgical Treatment of Lead and Zinc Materials
for
Critical Metal Production
Dr. Corby G. Anderson PE
Director, Kroll Institute for Extractive Metallurgy
Mining Engineering Department
Colorado School of Mines
Golden, Colorado USA
Lead- Zinc 2023
Changsha, China
October 20230
Colorado School of Mines
•Est. 1874
•Golden, Colorado
•21 Technical Majors
•About 200 Faculty
•About 7000 Students
•“…has a unique mission in energy,
mineral, and materials science and
engineering…”
•“has the most stringent admission
standards of any US public engineering
school.”
•“QS ranked #1 in the World for Mining
and Mineral Engineering” by Business
Insider.
•“Ranked as #1 US Engineering school”
by USA Today.
•“average starting salary of a BSc
Mines graduate is $ 10 K more
than an Ivy League graduate.”
Lead- Zinc 2023
Changsha, China
October 20230
Dr. Corby G. Anderson, PE
KIEM Director
Mining Engineering Department
Colorado School of Mines
Recent Research Partners:
Newmont Mining, Tata
Chemicals, Rio Tinto,
Freeport McMoran,
University of Wyoming,
University of Utah, NREL,
Ames Lab, Penn State,
UNSA, WPI, KU Leuven,
ORNL, INL, U of Tokyo,
Lundin Mining, Sibanye
Stillwater and many others !
Lead- Zinc 2023
Changsha, China
October 20230
A Research Center Located in the Department of Mining Engineering
•KIEM was established in 1974 using funds provided
by William Kroll who invented processes to produce
titanium and zirconium metal from ores.
•Over the years, the Kroll Institute has provided
support for a significant number of undergraduate
and graduate students who have gone on to make
important contributions to the mining, minerals and
metals industries.
•The objectives are to provide research expertise,
well-trained engineers to industry, and research and
educational opportunities to students, in the areas of
: minerals processing, extractive metallurgy,
recycling, and waste minimization.
Lead- Zinc 2023
Changsha, China
October 20230
Jihye Kim
Assistant Professor
Lead- Zinc 2023
Changsha, China
October 20230
The Kroll Institute for Extractive Metallurgy - KIEM
Department of Metallurgical and Materials
Engineering
Colorado School of Mines
www.mines.edu
KIEM
Lead- Zinc 2023
Changsha, China
October 20230
Nitrogen Species Catalyzed (NSC)
Leaching Fundamentals
3 MeS (S)+ 2HNO3 (Aq)+ 3H2SO4 (Aq) 3 MeSO4+ 3So (S) + 2NO (G) + 4H2O
NaNO2 (Aq) + H+HNO2 (Aq) + Na+
HNO2 (Aq) + H+NO+ (Aq) + H2O
2MeS (S) + 4NO+(Aq) 2Me+2 (Aq) + 2So+ 4NO (G)
Lead- Zinc 2023
Changsha, China
October 20230
Nitrogen Species Catalyzed (NSC)
Leaching Fundamentals
Relative Potentials of Hydrometallurgical Oxidizers.
E0h
Oxidant Redox Equation (pH = 0, H2ref.)
Fe+3 Fe+3 + e-Fe+2 0.770 V
HNO3NO3-+ 4H++3e-NO(g) + 2H2O 0.957 V
HNO2NO2 -+ 2H++ e-NO(g) + H2O 1.202 V
O2 (g) O2+ 4H++ 4e-2H2O 1.230 V
Cl2 (g) Cl2 (g) + 2e -2 Cl-1.358 V
NO+NO++ e-NO(g) 1.450 V
Lead- Zinc 2023
Changsha, China
October 20230
Nitrogen Species Catalyzed (NSC)
Leaching Fundamentals
2NO (G) + O2 (G) < --> 2NO2 (G)
2NO2 (G) <--> 2NO2 (Aq)
2NO2 (Aq) + 2NO (Aq) + 4H+<--> 4NO+ (Aq) + 2H2O
Lead- Zinc 2023
Changsha, China
October 20230
Nitrogen Species Catalyzed (NSC)
Leaching Fundamentals
2MeS (G) + 4H++ O2 (G) 2Me+2 (Aq) + 2So+ 2H2O
Lead- Zinc 2023
Changsha, China
October 20230
NSC Hydrometallurgical Treatment of a Gallium Concentrate
In an eventual industrial pilot plant scenario, slag concentrate f
from a smelting of a germanium zinc concentrate processing by
product was a candidate material.
An unoptimized NSC pressure oxidation leach was performed
on this material.
Lead- Zinc 2023
Changsha, China
October 20230
NSC Hydrometallurgical Treatment of a Gallium Concentrate
Total S, %Ge, %Ga, %Fe, %Zn, %
4.330.021.86
21.86
10.6
Composition of Gallium Slag.
Lead- Zinc 2023
Changsha, China
October 20230
NSC Hydrometallurgical Treatment of a Gallium Concentrate
UnitOperating Criteria
150 g/LInitial Free Sulphuric Acid
620 kPagReactor Working Pressure
100 g/LSlurry Solids Content
80% -10 micronSolids Size
105°CMaximum Temperature
2.0 g/LNitrogen Species Concentration
120 minReaction Time
Nitrogen Species Catalyzed Partial Oxidation Leach Conditions.
Lead- Zinc 2023
Changsha, China
October 20230
NSC Hydrometallurgical Treatment of a Gallium Concentrate
Fe, %Ge, %Ga, %Zn, %
43.690.9075.1675.21Solution
56.3199.1024.8425.79Residue
Mass Distribution of Nitrogen Species Catalyzed Partial Oxidation Leach Produc
t
Lead- Zinc 2023
Changsha, China
October 20230
NSC Pressure Oxidation of a
Lead Concentrate Base and Precious Metals.
A complex polymetallic lead and zinc orebody containing many other base metals
and gold and silver was to be developed.
It was desired to selectively leach base and precious metals from the concentrate
leaving behind a lead sulphide residue suitable for smelting.
Lead- Zinc 2023
Changsha, China
October 20230
NSC Pressure Oxidation of a
Lead Concentrate With Base and Precious Metals.
Lead Concentrate Elemental Analysis.
Pb, % Zn, % Co, % Cu, % Ni, % Ag g/T TS, % TC, %
21.6 2.66 0.81 2.02 0.66 53.0 18.9 8.5
Lead- Zinc 2023
Changsha, China
October 20230
NSC Pressure Oxidation of a
Lead Concentrate With Base and Precious Metals.
NSC Locked Cycle Conditions and Recoveries to Solution.
Locked Cycles = 7
Recycle Percentage = 25 %
Grind Time = 10 minutes
Initial Free Sulfuric Acid = 200 g/L
Reactor Working Pressure = 620 kPag
Slurry Solids Content = 100 g/L
Maximum Temperature = 130 C
Total Tine = 60 minutes
Nitrogen Species Concentration = 2.0 g/L
Copper Average Recovery = 95.1 %
Silver Average Recovery = 96.2 %
Cobalt Average Recovery = 97.3 %
Zinc Average Recovery = 98.4 %
Nickel Average Recovery = 96.8 %
Lead- Zinc 2023
Changsha, China
October 20230
Sodium sulfide, Na2S, is a very selective
lixiviant.
Only As, Hg, Sb, Au, Te and Sn have
significant solubilities.
Previously used in USA for copper
concentrate treatment and Sb production.
Used industrially for Sb production in USSR,
Australia and China.
Alkaline Sulfide Hydrometallurgy (ASL)
Lead- Zinc 2023
Changsha, China
October 20230
Antimony and Mercury are universally soluble.
Gold, Tin, Tellurium and Arsenic solubility is
dependent on mineralogy.
Some solubility of Silver depending on mineralogy.
Some minimal solubility of Copper and Iron.
Alkaline Sulfide Hydrometallurgy
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgy - Sulfur Stability Diagram.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgy
4S + 6OH-→ 2S2- + S2O32- + H2O
(X-1)S + S2- → S2-X(where X = 2 to 5)
SX2- + 2(X-1)e-→ xS2-
S22- + 2e-→ 2S2-
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Solutions
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgy - Sulfur Meta Stable Species Diagram.
Lead- Zinc 2023
Changsha, China
October 20230
Na2S + As2S3 2NaAsS2
NaAsS2 + Na2S Na3AsS3
1.5 H2O + 2 Na2S + ½ As2O3 NaAsS2+ 3 NaOH
NaAsS2 + Na2S Na3AsS3
Alkaline Sulfide Hydrometallurgy
Lead- Zinc 2023
Changsha, China
October 20230
Na2S + Sb2S3 2NaSbS2
NaSbS2 + Na2S Na3SbS3
1.5 H2O + 2 Na2S + ½ Sb2O3 NaSbS2+ 3 NaOH
NaSbS2 + Na2S Na3SbS3
Alkaline Sulfide Hydrometallurgy
Lead- Zinc 2023
Changsha, China
October 20230
Na2S + HgS Na2HgS2
Na2S+ Hg2S 2 NaHgS
Alkaline Sulfide Hydrometallurgy
Lead- Zinc 2023
Changsha, China
October 20230
Na2S + SnS2 Na2SnS3
H2O + 2 Na2S + SnO Na2SnS2+ 2 NaOH
Alkaline Sulfide Hydrometallurgy
Lead- Zinc 2023
Changsha, China
October 20230
Overall Reaction
2Au + S22- + 2S2- → 2AuS-+2S2-
Alkaline Sulfide Gold Recovery
Process
Lead- Zinc 2023
Changsha, China
October 20230
5M Sulfur - 100ppm Au - 1ATM - Final Stability
Alkaline Sulfide Gold Recovery
Process
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Gold Separation and
Recovery Processes
• Electrowinning
• Cementation
• Gaseous Precipitation
• Chemical Precipitation
• Solvent Extraction
• Ion Exchange
Lead- Zinc 2023
Changsha, China
October 20230
Recovery: Electrowinning
Example Gold Recovery From Solution
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Gold Pilot Plant
Lead- Zinc 2023
Changsha, China
October 20230
Precious Metal Recovery Processes
Alkaline Sulfide Waste Solution Treatment
2 O2 + Na2S Na2SO4
3.5 O2 + 2 NaOH + Na2S22 Na2SO4+ H2O
8 O2 + 8 NaOH + Na2S55 Na2SO4+ 4 H2O
2 NaOH + 2 O2 + Na2S2O3 2 Na2SO4+ H2O
Lead- Zinc 2023
Changsha, China
October 20230
Sodium Sulfate Pressure Oxidation
Lead- Zinc 2023
Changsha, China
October 20230
Sulfuric Acid and Caustic Production from Sodium Sulfate.
Na2SO4 Splitting Through Electrodialysis
Lead- Zinc 2023
Changsha, China
October 20230
Na2SO4Splitting Through Electrodialysis
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Lead Smelter
Copper Dross Flue Dust
The formation of arsenic and antimony laden dusts in the
processing of lead is commonly encountered.
An example of hydrometallurgical treatment of
this arsenic trioxide bearing material follows.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Lead Smelter
Copper Dross Flue Dust
Copper Dross Flue Dust Head Sample Assay
In, % Pb,% Sb,% As,% Zn,%
0.3 46.0 9.0 12.0 11.0
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Lead Smelter
Copper Dross Flue Dust
Leach Testing Conditions.
Leach Time = 6 Hr.
Percent Solids = 25%
Leach Temperature = 105 C
Sulfide Concentration = 100 g/L
Free Hydroxide Concentration = 10 g/L
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Lead Smelter
Copper Dross Flue Dust
Leach Test Results
% of Metal Leached
In, % Pb,% Sb,% As,% Zn,%
0.0 0.0 95.0 99.0 0.0
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of
Lead Smelter Tin Removal Salt.
The presence of tin in lead smelters is a common occurrence and poses problems.
Alkaline sulfide hydrometallurgy can be effective
in treating these types of smelter waste.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of
Lead Smelter Tin Removal Salt.
Lead Smelter Tin Salt Head Sample Assay
Pb % As % Sb % Sn %
76.3 0.20 0.53 8.20
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of
Lead Smelter Tin Removal Salt.
Leach Testing Conditions
Leach Conditions: Time = 8 Hr
Solids = 5%
Temperature = 90OC
Total Sulfur Concentration = 50 g/L
Free Hydroxide Concentration = 0 g/L Leach
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of
Lead Smelter Tin Removal Salt.
Leach Test Results
% of Metal Leached
Pb % As % Sb % Sn %
0.0 100.0 100.0 91.1
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of Lead Smelter Speiss.
The formation of speiss in lead smelters is a common
occurrence and poses problems.
Significant levels of precious metals are accumulated in the
resultant arsenides and antimonides.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of Lead Smelter Speiss.
Lead Smelter Speiss Head Sample Assay
Cu,% Ni,% Sn,% Cd,% As,% Sb, % Pb,% Fe,% Zn,% Au g/T, Ag, g/T
43.5 1.4 0.5 0.1 12.2 3.3 14.8 1.7 0.9 45.0 9000
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of Lead Smelter Speiss.
Leach Testing Conditions
Leach Time = 6 Hr.
Percent Solids = 25%
Leach Temperature = 105O C
Total Sulfur Concentration = 100 g/L
Free Hydroxide Concentration = 25
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment of Lead Smelter Speiss.
Leach Test Results
% of Metal Leached
Cu,% Ni,% Sn,% Cd,% As,% Sb, % Pb,% Fe,% Zn,% Au %, Ag %
0.0 0.0 2.0 0.0 99.1 99.4 0.0 0.0 0.0 9.1 0.0
Lead- Zinc 2023
Changsha, China
October 20230
Applications of Alkaline Sulfide Hydrometallurgy
to a Lead Concentrate with Antimony, Arsenic,
Gold Silver and Mercury.
As a further example of the flexibility of the alkaline
sulfide leaching technology the following summary
is presented.
In this case, an industrial lead concentrate producer
wished to leach as much antimony, mercury, gold
and silver as possible before shipping to a smelter.
Lead- Zinc 2023
Changsha, China
October 20230
Applications of Alkaline Sulfide
Hydrometallurgy to a Lead Concentrate with
Antimony, Arsenic, Gold Silver and Mercury.
Table 12 - Concentrate Composition (%)
TS,
%
Ag,
g/tonne
Au,
g/tonne
PbHgAsSb
32.02000.4640.6
46.10.11
0.85
5.3
Lead- Zinc 2023
Changsha, China
October 20230
Applications of Alkaline Sulfide Hydrometallurgy
to a Lead Concentrate with Antimony, Arsenic,
Gold Silver and Mercury.
Table 13 - Alkaline Sulfide Leach
Results (%)
Sb As Hg Pb Au Ag
95.4 86.3 95.2 0.0 78.30 19.3
Leach Conditions: Time = 8 Hr,
Concentrate = 100 g/L, Temperature
= 100
O
C, Sulphide Addition =50 g/L,
Sulphur Addition 5 g/L, Sodium
Hydroxide = 10 g/L
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment
of Mercury Bearing Tetrahedrite.
In many parts of the world, tetrahedrite, Cu12Sb4S13
occurs as a primary copper and silver bearing mineral.
Often these contain mercury along with antimony and arsenic.
Alkaline sulfide hydrometallurgy can be effective
in treating these types of ores and concentrates.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment
of Mercury Bearing Tetrahedrite.
Roznava Tetrahedrite Concentrate Composition
Sb% As% Hg% Cu% Fe% Au, g/T Ag, g/T TS,
17.3 1.8 0.55 26.1 12.4 6 4002.0 22.0
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment
of Mercury Bearing Tetrahedrite.
Leach Testing Conditions
Leach Time = 6 Hr.
Percent Solids = 25%
Leach Temperature = 105OC
Total Sulfur Concentration = 100 g/L
Free Hydroxide Concentration = 25
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical Treatment
of Mercury Bearing Tetrahedrite.
Leach Test Results
% of Metal Leached
Sb% As% Hg% Cu% Fe% Au, % Ag, %
95.0 60.0 95.0 0.0 0.0 20.0 2.0
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Arsenic Bearing Ores and Concentrates.
In many parts of the world, enargite, Cu3AsS4,
occurs as a primary copper mineral.
Alkaline sulfide hydrometallurgy can be effective
in treating these types of ores and concentrates.
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Arsenic Bearing Ores and Concentrates.
Copper Enargite Concentrate Head Sample Assay
Cu, % As, % Sb, % Au, g/T
30.1 10.7 1.2 35.1
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Arsenic Bearing Ores and Concentrates.
Leach Testing Conditions
Leach Time = 1 Hr.
Percent Solids = 25%
Leach Temperature = 105 C
Sulfide Concentration = 100 g/L
Free Hydroxide Concentration = 10 g/L
Lead- Zinc 2023
Changsha, China
October 20230
Alkaline Sulfide Hydrometallurgical
Treatment of Arsenic Bearing Ores and Concentrates.
Leach Test Results.
% of Metal Leached
Cu, % As, % Sb, % Au, %
0.0 99.2 99.7 14.3
In this case, a high grade, 38% copper concentrate with
minimal arsenic was produced for treatment by smelting.
Lead- Zinc 2023
Changsha, China
October 20230
Hydrometallurgical Treatment of Lead and Zinc Materials
for
Critical Metal Production
Thank You !
Questions ?
Lead- Zinc 2023
Changsha, China
October 20230
Hydrometallurgical Treatment of Lead and Zinc Materials
for
Critical Metal Production
Dr. Corby G. Anderson PE
Director, Kroll Institute for Extractive Metallurgy
Mining Engineering Department
Colorado School of Mines
Golden, Colorado USA