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Prof. Leandro Voisin A, MSc., Dr. Pyrometallurgy Laboratory - Director
DIMIN MSc. - Coordinator AMTC - Senior Researcher
New Strategies for the Treatment of Copper Concentrates with High Arsenic Content in Chile
Contents
1. Chile a Mining Country - World and local production and reserves for copper - Mining companies in Chile - Copper products generated in Chile
2. Smelters located in Chile - World and local production for smelter copper
- Smelters in Chile - Technologies of copper smelters in Chile
3. Environmental standard for air pollutant emissions in Chile - OECD Environmental Working Papers - New Standard for S & As emitted by smelters in Chile - Current situation and environmental commitments
4. Solutions for the treatment of As emissions in Chile - Present solutions - Future strategies
2
Chile a Mining Country, 2011 World
Production Reserves Production Reserves Ranking, No
Metallic Mining
Copper 5.263.000 190.000.000 32,4 27,5 1
Molybdenum 38.000 1.200.000 15,2 12,0 3
Rhenium 26 1.300 53,1 52,0 1
Silver 1.400 70.000 5,9 13,2 5
Gold 45 3.400 1,7 6,7 14
Industrial Minerals
Natural Nitrates 1.189.600 1.189.600 100 100 1
Lithium 12.6000 7.500.000 37,1 57,7 1
Iodine 18.000 9.000.000 62,1 60,0 1
Metric Tonnes World Participation, %
Cu Production
Chile32%
Peru8%
China7%
USA7%
Australia6%
Zambia5%
Russia4%
Indonesia4%
Canada3%
Congo3% Other
21%Chile28%
Peru13%Australia
12%
Mexico6%
USA5%
China4%
Russia4%
Indonesia4%
Poland4%
Zambia3%
Other17%
Cu Reserves
Source: USGS & COCHILCO / Chilean Copper Commission, Reports 2011
4
Chile has a coastline of 6435 kms in length, and in its northern (first 2100 kms. of extension), over 33 large mining projects are being developed.
Large Mining Operations (First path 1100 kms. from the north)
TARAPACA PROD. COMPANY PROPERTYCerro Colorado C BHP Bi l l i ton Pampa Norte BHP Bi l l i ton
Doña Inés de
Col lahuas i C M
Cía. Minera Doña Inés de
Col lahuas i
Anglo American plc (44%), Xstrata Copper (44%)
& JCR (12%)
Quebrada Blanca CCía. Minera Quebrada
Blanca
Teck (76,5%), Invers iones Mineras S.A. (13,5%)
& Enami (10%)
ANTOFAGASTA PROD. COMPANY PROPERTY
El Abra C SCM El Abra FCX (51%) & Government of Chi le (49%)
Radomiro Tomic C Codelco Government of Chi le
Chuquicamata C G S Codelco Government of Chi le
Michi l la C Minera Michi l laAntofagasta plc (74,2%),
Invers iones Costa Verde (15,3%) & Others .
Spence C BHP Bi l l i ton Pampa Norte BHP Bi l l i ton
El Tesoro C Minera El Tesoro Antofagasta plc (70%) & Marubeni Corp. (30%)
Esperanza C G Minera Esperanza Antofagasta Minera ls (70%) & Marubeni Corp. (30%)
Gaby C Codelco Estado de Chi le Government of Chi le
Mantos Blancos C Anglo American Norte Anglo American plc
Lomas Bayas CCía. Minera Xstrata Lomas
BayasXstrata Copper
Zaldívar C Cía. Minera Za ldivar Barrick
Escondida C Minera Escondida Ltda BHP Bi l l i ton (57,5%), Río Tinto (30%) & JECO (12,5%)
Altonorte CComplejo Metalúrgico
Al tonorteXstrata Copper
El Peñón G S Minera Meridian Yamana Gold
Chile a Mining Country
C : COPPER M: MOLYBDENUM G: GOLD S: SILVER
5
ATACAMA PROD. COMPANY PROPERTY
Mantoverde C Anglo American Norte Anglo American plc
Salvador C M Codelco Government of Chi le
La Coipa G S Cía. Minera Mantos de Oro Kinross
Maricunga G Cía. Minera Maricunga Kinross
Ojos del Sa lado C G CCM Ojos del Sa lado FCX (80%) & Sumitomo Corp. (20%)
Candelaria C G CCM Candelaria FCX (80%) & Sumitomo Corp. (20%)
Caserones C MSCM Minera Lumina Copper
Chi lePan Pacific Copper
COQUIMBO PROD. COMPANY PROPERTYCarmen de
Andacol loC
Cía. Minera Teck Carmen de
Andacol loTeck (90%) & Enami (10%)
Los Pelambres C M Minera Los PelambresAntofagasta plc (60%),
Nippon LPR BV (25%) & MM LP Holding (15%)
VALPARAISO PROD. COMPANY PROPERTYVentanas C G S Codelco Government of Chi le
El Soldado C Anglo American Sur Anglo American plc (50,1%),
JV Codelco-Mitsui (29,5%) & Mitsubishi Corp. (20,4%)
Chagres C Anglo American Sur Anglo American plc (50,1%),
JV Codelco-Mitsui (29,5%) & Mitsubishi Corp. (20,4%)
Andina C M Codelco Government of Chi le
METROPOLITANA PROD. COMPANY PROPERTY
Los Bronces C M Anglo American Sur Anglo American plc (50,1%),
JV Codelco-Mitsui (29,5%) & Mitsubishi Corp. (20,4%)
Florida G S Minera Florida Yamana Gold
BDO. O´HIGGINS PROD. COMPANY PROPERTY
El Teniente C M Codelco Government of Chi le
Large Mining Operations (Second path, 1100 to 2100 kms. from the north)
Chile a Mining Country
C : COPPER M: MOLYBDENUM G: GOLD S: SILVER
6
0
5
10
15
20
25
30
35
40
45
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
World Production Chilean Production
National Production (CODELCO) Chilean Participation
National Participation (CODELCO)
Cu Content
(kMT)
(%) World
Participation
Year
World & Chilean Copper Production & Participation (1950 – 2011)
(kMT Copper Content and % of the World)
7
Copper Production in Chile by 2011 (kMT Copper Content)
By company
CODELCO 1796
Antofagasta Minerals 422
Inversiones Mineras S.A. 9
ENAMI 6
BHP Billiton 745
Anglo American 463
Xstrata 273
Rio Tinto PLC 245
Freeport-McMoRan Inc. (FCX) 182
Barrick 132
Teck 49
Others 395
Japan Collahuasi Resources (JCR) 132
Mitsubishi 118
Nippon LP 107
Japan Escondida Corporation (JECO) 102
Marubeni 58
Sumitomo 30
Codelco34%
BHP Billiton14%
Anglo American 9%
Antofagasta Minerals 8%
Xstrata 5%
Rio Tinto PLC 5%
FCX 3%
Barrick 3%JCR 3% Mitsubishi 2%
Others14%
JCR24%
Mitsubishi22%
Nippon LP19%
JECO19%
Marubeni11%
Sumitomo5%
CHILEAN 2233
JAPANESE 547
FOREING PRODUCTION 2483
TOTAL PRODUCTION 5263
Copper Mine Production 2011
8
5,263
1,364
2,025
999
69
3238
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
6000
Chilean Copper Products 1991-2011 (kMT Copper Content)
Mine
Smelter (1)
SX-EX Cathodes
ER Cathodes RAF
Cu Content (kMT)
Year
(1) Includes blister copper and copper anodes.
Source: COCHILCO / Chilean Copper Commission, based on company reports.
CONCENTRATES
9
Chilean Copper Exports by Product Type 2011 5263 kMT of copper content was produced and 5070 kMT was exported.
By product By destination
Cu
Co
nte
nt (k
MT
) Pa
rticip
atio
n (%
)
Year
JAPAN
10
0
1000
2000
3000
4000
5000
6000
Chilean Copper Concentrate 1991-2011 (kMT Copper Content)
Mine Production
Exported to Japan
Cu Content (kMT)
Year
Source: COCHILCO / Chilean Copper Commission, based on company reports.
Exported to Others
Processed in Chile
3238 kMT of Copper Concentrate was produced in Chile by 2011
Processed Exported to Japan Exported to Others
kMT 1538 593 1107
% 47.5 18.3 34.2
11
Major Challenges for Chilean Mining Production
12
INNOVATION
&
TECHNOLOGY
Environmentally Friendly
GEOLOGY
•decreasing ore grades
• Increasing impurity contents
•deeper mine sites
→incentive to exploration
(geological maps,
specialist staff, etc)
WATER • Increasing demand due to
increased mining production
•competition with other
sectors
→management for the
shortage
ENERGY
•High demand for electricity
• Increased energy costs
→National energy strategy
Mineralogy of Chilean Copper Concentrates, mass%
El Salvador Chuquicamata Andina Escondida
Chalcopyrite CuFeS2 7.5 12 81 4.8
Chalcosite Cu2S 21 11.2 1.5 53
Covellite CuS 14 17 1.1 0.6
Bornite Cu5FeS4 1.51 1.65 0.27 0.11
Enargite Cu3AsS4 2.1 5.3 0.6 0.36
Piyrite FeS2 38 35 6.2 30
Molybdenite MoS2 0.29 0.89 0.29
Metallic Cu Cu 0.46 0.16
Cuprite Cu2O 0.5
Hematite Fe2O3 0.2 0.08
Others, Gangue 15.44 17.7 7.9 10.07
TOTAL 100 100 100 100
Mineral, Ore
Source: Based on company reports by 2011.
13
Principal Primary Copper Smelters in the World
Source: Flash Smelting Book, W.G. Davenport, E.H. Partelpoeq 15
There are 7 smelters located in Chile, 5 of them belong to the government.
Smelters in Chile
ANTOFAGASTA PROD. CONCETRATE SUPPLIER PROPERTY
Chuquicamata B A CChuquicamata, Radomiro
Tomic, Ministro HALESCodelco, Government of Chi le
Altonorte A Third parties Xstrata Copper
VALPARAISO PROD. CONCETRATE SUPPLIER PROPERTYVentanas B A C Third parties Codelco, Government of Chi le
Chagres A Soldado & Los BroncesAnglo American plc (50,1%),
JV Codelco-Mitsui (29,5%) & Mitsubishi Corp. (20,4%)
BDO. O´HIGGINS PROD. CONCETRATE SUPPLIER PROPERTYCaletones B A R El Teniente, Andina Codelco, Government of Chi le
B: BLISTER A: ANODE C: CATHODE R: FIRE REFINING
16
ATACAMA PROD. CONCETRATE SUPPLIER PROPERTYPotreri l los B A C Codelco Codelco, Government of Chi le
Paipotes, HVL A Third parties Enami, Government of Chi le
0
2
4
6
8
10
12
14
16
0
2000
4000
6000
8000
10000
12000
14000
16000
World Production Chilean Production Chilean Participation
Cu Content
(kMT)
(%) World
Participation
Year
World & Chilean Smelter Copper Production & Participation (1950 – 2011)
(kMT Copper Content and % of the World)
17
World Ranking Copper Smelters in terms of the Production of Copper Content 2011
Source: BROOK HUNT Cu Content (kMT)
POSITION
18
Copper Concentrate of the Smelters Located in Chile, 2010
CODELCO XSTRATA CODELCO ENAMI CODELCO (1) ACMM CODELCO
Chuquicamata Altonorte Potrerillos Paipotes Ventanas Chagres Caletones
TREATMENT (TPY) 1650000 800000 680000 330000 420000 610000 1600000
PARTICULE SIZE (m) 80% < 104 - 80% < 173 80% < 53 70% < 74 76% < 43 70% < 43
H2O(%) WET CONC. - 8.42 8 7.5 - 9 8.6 10 8.5
H2O(%) DRY CONC. 0.2 - 0.2 - - - 0.2
CONCENTRATE
COMPOSITION (%)
Cu 33 36.6 30.8 28 - 30 30.7 31 30.8
Fe 20 15 23 28 - 30 25.3 22.4 26.5
S 32.9 28.2 31.2 32 - 35 32.4 31 31.8
SiO2 6.2 - 7.7 1.8 - 2.5 6.9 6.6 5.5
As 0.83 - 0.31 0.06 0.08 0.19
Sb - - 0.04 0.005 0.23
Bi 0.08 - 0.01 - -
Pb 0.18 - 0.01 0.007 0.045
Zn 1.28 - 0.22 0.03 0.22
Mo 0.19 - 0.17 0.09 0.15
Ni 0.01 - 0.01 - 0.004
Ag (ppm) 110 - 75
Au (ppm) 0.5 - 1.5
(1) ACMM: Anglo American, Codelco, Mitsui & Mitsubishi
Source: Based on company reports by 2010. 19
Smelters in Chile & their Capacities for Treating Copper Concentrate
CODELCO XSTRATA CODELCO ENAMI CODELCO (1) ACMM CODELCO
Chuquicamata Altonorte Potrerillos Paipotes Ventanas Chagres Caletones
STARTED YEAR 1952 1993 1927 1952 1965 1960 1922
SMELTING 1 T + 1 F N 1 T 1 T 1 T 1 F 2 T
SIZE, L x D (m) 22 x 5 26.4 x 5.3 22 x 5 14.9 x 3.8 14 x 5 - 22 x 5
CAPACITY
design (TPD) 2500 (2400) - 2200 - 1200 - 2600
nominal (TPD) 2200 (2650) 2800 2000 1050 1400 1890 2300
annual (TPY)748000 (902000) 950000 680000 357000 450000 610000 1600000
CONVERTING 4 CPS 3 CPS 3 CPS 1 CPS 3 CPS 4 CPS 3 CPS
FIRE REFINING 6 A + 2 SC 3 A 2 A 1 A 1 A + 2 R 2 A 3 A + 3 R
SLAG CLEANING 1 ESC + 1 SC Flotation 3 SC 1 ESC 1 ESC 1 Cylind. 4 SC
CASTING WHEEL 3 Out 2 Out 2 Demag 1 Out 1 Walker 1 Out 2 Out
(1) ACMM: Anglo American, Codelco, Mitsui & Mitsubishi
F: Outokumpu Flash Furnace
T: Teniente Converter
CPS: Peirce Smith Converter
A: Anode Furnace
ESC: Electric Slag Cleaning Furnace
SC: Slag Cleaning Furnace
OPERATION UNIT
Chuquicamata26%
Caletones22%
Potrerillos11%
Paipotes, 5%
Ventanas, 7%
Altonorte20%
Chagres, 9%
Participation (%)
20
OECD Environmental Working Papers
Source: Hunt, A. (2011), “Policy Interventions to Address Health Impacts Associated with Air Pollution, Unsafe Water Supply and Sanitation, and Hazardous Chemicals”, OECD Environment Working Papers, No. 35, OECD Publishing.
http://dx.doi.org/10.1787/5kg9qx8dsx43-en
25
OECD Environmental Working Papers
Source: Hunt, A. (2011), “Policy Interventions to Address Health Impacts Associated with Air Pollution, Unsafe Water Supply and Sanitation, and Hazardous Chemicals”, OECD Environment Working Papers, No. 35, OECD Publishing.
http://dx.doi.org/10.1787/5kg9qx8dsx43-en 26
On July 3, 2012, the Ministry of Environment of Chile, established the new policy which legislate the emissions SO2 and pollutants generated by the copper smelters which objective is to protect the health of people and the environment around the country.
New Environmental Standard for SO2 & As emitted by smelters in Chile
In 2005, the assessment of environmental performance of Chile prepared for the OECD concluded that “Smelting activities are still responsible for the highest emission and should reduce even more“ recommending developing emission standards for reducing sulfur dioxide and toxic pollutants.
As a result of its implementation will reduce emissions air of PM, SO2, As and Hg.
27
New Environmental Standard for SO2 & As emitted by smelters in Chile
Pollutants that are regulated on the New Environmental Policy: Fugitive emissions, SO2, As, MP, Hg Smelting & Converting Emissions by chimney, SO2, As, MP, Hg Unit Operations Acid mists, SO2 & SO3 Acid plants Stock piles, MP Concentrate stockpiles
28
New Environmental Standard for SO2 & As emitted by smelters in Chile
29
Global, measured by year (%) (*) Existing Sources SO2 > 95 As > 95 (*) Existing 7 Copper smelters + the new roasting plant of Ministro Hales Mine, Codelco.
New Sources (from July 3, 2012) > 98 > 99.98
Per Unit Operation, measured by mass balance mg/Nm3:
Smelting Converting Drying Slag
Cleaning Fire
Refining Acid Plant
MP = 50 (30)
Fugitive Emissions
MP = 50 (30) As = 1 (1)
SO2 = 2080 (520) As = 1 (1) Hg = - (0.1)
30
Chuquicamata Caletones Potrerillos Paipotes (*) Ventanas (*) Altonorte (*) Chagres
Concentrate (kTPY) 1650 1600 680 357 450 1160 610
SO2 Emissions (TPY) 96500 124500 89500 24500 19000 24000 13950
As Emissions (TPY) 812 365 790 35 107 128 107
Capture of SO2 (%) 91 88 83.5 89.4 93.8 93.7 95.7
New Environmental Standard for SO2 & As emitted by smelters in Chile
BASE LINE 2010
0 50000 100000 150000
Chuquicam…
Caletones
Potrerillos
Paipotes
(*) Ventanas
(*) Altonorte
(*) Chagres
Ministro …NEW POLICY
BASE LINE 2010
0 200 400 600 800 1000
Chuquica…
Caletones
Potrerillos
Paipotes
(*) …
(*) …
(*) Chagres
Ministro …NEW POLICY
BASE LINE 2010
POLLUTANT RED.
TPY
%
204142
52
1357
58
SO2 As
SO2 As
TPY
New Environmental Standard for SO2 & As emitted by smelters in Chile
In 2010, 391950 TPY of SO2 and 2344 TPY of As, were emitted to the air by the copper smelter located in Chile.
According to the new environmental policy, the captures of SO2 and As have to be at least 95% each one for the existing sources. In the case of new sources those values must fulfill at least 98% and 99.98%, respectively.
Chuquicamata, Potrerillos, Paipotes and Caletones must reach the standard in 5 years while the other 3 smelters in 2.5 years because they have system of double absorption contact in their acid plants.
By 2017, the emissions of SO2 and As will be reduced to 187808 and 987 TPY or 52 and 58% , respectively, compared to the base line.
31
SO2 (%) As (%)
Codelco 84.1 88.5
Enami 6.3 1.5
Privates 9.7 10.0
35
FLOTATION
COMMINUTION
Sulphide Ores
SLAG
CLEANING
Recovered matte
slag
slag
Air + O2
Air
Air
Flux
Reductant
gas,dust
ACID PLANT
Reverts
discard slag slag Reverts
gas, chimney
I PM
gas,dust
I PM
I PM
SMELTING
CONVERTING
REFINING
Copper
anodes
Copper matte
Blister copper
Copper
concentrates
Demand for more complex ores with higher contents of
As and Sb has generally been high
Amounts of As and Sb in produced metals have far
exceeded the demand
Some ores high in As and Sb have in fact faced a cost penalty at the
smelter, or are deliberately avoided during mining
Elimination of these elements before
final refining stage is required
Extracting Copper from Sulphide Ores
4.1 EcoMetales Limited Since 2007, PTPA Flue Dust Treatment and As and Sb Abatement Plant
• Smelter Dust Leaching (PTP, 2007)
The dust is acid leached producing copper PLS which is pumped 7 kms to Codelco’s Chuquicamata Division where it is used to produce copper cathodes The leaching waste (7 % Cu) is dried and conditioned before being returned to the smelter in dump trucks for processing. Since 2007 the PTP plant has processed 270 kT of dust and recovered 48 kT of Copper. It currently processes dust from Codelco’s Chuquicamata, Potrerillos and Ventanas smelters. 36
Cu As Sb Bi Pb S Fe
15 -30 4 - 17. 0.1 - 1.5 0.1 - 0.9 0.2 - 20 0.8 - 13 0.5 - 12
Smelter Dust (composition, mass%)
• Arsenic and Antimony Abatement (2012) The AAA project takes the copper-rich solution produced by the acid leaching of dust and refinery effluents and subjects it to three consecutive treatments: Stage I: Oxidization of the arsenic (+III to +V); Stage II: pH adjustment; Stage III: Precipitation with ferric sulfate (produced in a own plant from magnetite and sulfuric acid). The AAA process uses technology that allows to stabilize As on an industrial scale as. scorodite generated at atmospheric pressure The AAA project was designed to abate up to 10 kTPY of As and recover over 25 kTPY of Cu.
37
4.1 EcoMetales Limited Since 2007, PTPA Flue Dust Treatment and As and Sb Abatement Plant
4.2 Recovery of copper from complex slag by flotation
Smelting complex copper slag
- CURRENT PROBLEMS: - Traditional slag cleaning processes, ESC or SC.
- High operational costs - Electricity and/or hydrocarbons, - Environmental problems, - Low efficiency (Cu losses 1%)
- SUPPORT: - CODELCO, ENAMI & ANGLO AMERICAN's
smelters have expressed interest.
- RESEARCH: - Optimal operational conditions
- Particle size - Collector type and concentration - pH and Others - Technical and economic assessment
- CFD modeling, including mass transfer CFD Modeling
Applied R&D Project TECHNOLOGICAL INNOVATION
38
39
4.3 Continuous Converting of Copper Matte in Packed Bed Reactor
Refractory ladge to receive liquid matte
Refractory ladge for distribution of matte
Gas (SO2) + dust
Gas (SO2) + dust
Flux
BURNER BURNER
BURNER
Load measuring cells
Packed bed refratories (Cr2O3 – MgO [2»f])
TUYERS TUYERS
Air/O2 Air/O2
PACKED BED REACTOR FOR CONTINUOUS CONVERTING
Slag receptor Blister receptor
40
Higher treatment capacity [Capacity to treat 5 tph in one pilot reactor of 1.8 x 1.2 m (h x f) compared to a 20 tph processed by the current industrial plant using 1 CPS reactors of CPS of 12 x 4 m (l x f)]. Continuous production of blister copper in one steep in comparison to the batch current process which considers two steeps of slag-forming and copper-making, respectively. Reduction of fugitive gases emissions.(High environmental impact) and also reduction of refractory consumption. Higher converting efficiency and decreasing of process time.
4.3 Continuous Converting of Copper Matte in Packed Bed Reactor
Smelting Furnace
Fluxing System
CCE Furnace
Blister Copper
Samplin Crucible
CCE Furnace
Laboratory Test
CFD Modeling
Industrial Pilot Plant
Smelting Furnace
CURRENTLY - Market assessment - IP status and assessments
SUPPORT - ENAMI funding by 2012:
- Laboratory experiments - CFD modeling - Setup of an Industrial-Pilot plant
RESEARCH - Future work (2013):
(U. of Chile, ENAMI, Buildtek) - Process Optimization - Pilot-Plant tests - R&D Packaging and Transfer
Applied R&D Project TECHNOLOGICAL INNOVATION
4.3 Continuous Converting of Copper Matte in Packed Bed Reactor
42
To replace the simple absorption contact plant by double contact ones.
To replace the SC and ESC furnaces by slag flotation.
Feeding a calcined product (high impurity concentrate) coming from the roasting plant of Ministro Hales Mine together with low arsenic copper concentrate to the Flash Furnace.
Trying a Olivine slag in the smelting stage in order to concentrate a larger amount of arsenic and antimony in that phase.
Trying the use of Speiss by adding Pig Iron in order to generate a condensed stable Iron-rich phase containing arsenic and antimony.
To innovate on continuous processes (The future of the Teniente converter is uncertain)
Other Step & Solutions for the
treatment of As emissions in Chile