new strategies for the treatment of copper concentrates...

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%),


Andina C M Codelco Government of Chi le

METROPOLITANA PROD. COMPANY PROPERTY

Los Bronces C M Anglo American Sur Anglo American plc (50,1%),


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

2. Smelters Located in Chile

14

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%),


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

CODELCO, Chuquicamata Copper Smelter

21

CODELCO, Caletones Copper Smelter

22

XSTRATA, Altonorte Copper Smelter

23

3. Environmental Standard for SO2 & As air emissions in Chile

24

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

http://dx.doi.org/

http://dx.doi.org/

http://dx.doi.org/

http://dx.doi.org/

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

http://dx.doi.org/

http://dx.doi.org/

http://dx.doi.org/

http://dx.doi.org/

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


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


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


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


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

4. Solutions for the treatment of

As emissions in Chile

34

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.


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


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

¡ Muchas Gracias！

どうもありがとうございました！

new strategies for the treatment of copper concentrates...

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