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CONTENTS Preface Preface to the Third Edition Preface to the Second Edition Preface to the First Edition Extracting Copper from Copper-Iron-Sulfide Ores Melting and Casting Cathode Coppe

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- 4

0

cd

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12

Mg

Ca

24.305 Magnesium

20

40.08 Calcium

56

137.33 BariWll

88

226.0254 Radium

3(IIIA) 4(IVA) 5 ( V A ) 6(VIA) 7(VIIA) 8 9(VIIIA)

57

138.9055 178.4, 180.947, 183.85 Lanthanum Hafnium Tantalum Wolfram

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18 (WIE

2

4.00260 Helium

17

35.453 Chlorine

35

79.904 Bromine

18

39.94, Argon

83.80 Krypton

54

131.30 Xenon

13 (IIIB) 14 ( N B )

10.81 12.011

A1 26.98154 28.085, Boron Silicon

67

Ho

164.9304 Holmium

65

Tb 158.9254 Terbium

71

Lu

Lr

174.96, Lutetium

I03

(260)

Lawrencium

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Extractive Metallurgy

of Copper

FOURTH EDITION

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Elsevier Titles of Related Interest

P BALAZ (Slovak Academy of Sciences, Slovakia)

Extractive Metallurgy of Activated Minerals

2000, Hardbound, 290 pages

ISBN: 0-444-50206-8

K.H.J BUSCHOW (University of Amsterdam, The Netherlands)

R.W CAHN (University of Cambridge, UK)

M.C FLEMINGS (Massachusetts Institute of Technology, M , USA)

B ILSCHNE (Swiss Federal Institute of Technology, Switzerland)

E.J KRAMER (University of California, CA, USA)

S MAHAJAN (Arizona State University, AZ, USA)

The Encyclopedia of Materials: Science and Technology

2001, Hardbound, approx 10000 pages

ISBN: 0-08-043 152-6 (1 1 -volume set)

Electronic version is also available:

http://www.elsevier.com/emsat/show/index htt

R.W CAHN (University of Cambridge, UK)

P HAASEN (University of Gottingen, Germany)

Physical Metallurgy, 4th Revised and Enhanced Edition

1996, Hardbound, 2888 pages

ISBN: 0-444-89875-1 (3-volume set)

V.S.T CIMINELLI (Universidade Federal de Minas Gerais, Brazil)

0 GARCIA Jr (UNESP-Campus Araraquara, Brazil)

Biohydrometallurgy: Fundamentals, Technology and Sustainable Development, Parts A and B

2001, Hardbound, 1348 pages

ISBN: 0-444-50623-3

Y MUKAKAMI (Kyushu University, Japan)

Metal Fatigue: Effects of Small Defects and Nonmetallic Inclusions

2002, Hardbound, 380 pages

ISBN: 0-08-044064-9

W PETRUK (Ottawa, Canada)

Applied Mineralogy in the Mining Industry

2000, Hardbound, 286 pages

ISBN: 0-444-50077-4

s to search for more Elsevier books, visit the Books Butler at

http://www.elsevier.com/homepage/boo ksbu tlerl

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Phelps Dodge Mining Company

Phoenix, AZ, USA

M SCHLESINGER

Metallurgical Engineering Department

University of Missouri - Rolla

Rolla, MO, USA

A.K BISWASt

FOURTH EDITION

PERGAMON

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ELSEVIER SCIENCE Ltd

T h e Boulevard, Langford L a n e

Kidlington, Oxford OX5 IGB, UK

0 2002 Elsevier Science Ltd All rights reserved

This work is protected under copyright by Elsevier Science, and the following terms and conditions apply to its use: Photocopying

Single photocopies of single chapters may be made for personal use as allowed by national copyright laws Permission of the Publisher and payment of a fee is required for all other photocopying, including multiple or systcrnatic copying, copying for advertising or promotional purposes, resale, and all forms of document delivery Special rates are available for educational institutions that wish to make photocopies for non-profit educational classroom use

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In the USA, users may clear permissions and make payments through the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA; phone: (+1) (978) 7508400, fax: ( + I ) (978) 7504744, and in the UK

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Notice

No responsibility is assumed by the Publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein Because of rapid advances in the medical sciences, in particular, independent verification of diagnoses and drug dosages should be made

First edition 1916

Second edition 1980

Third edition 1994

Fourth edition 2002

British Library Cataloguing in Publication Data

Davenport, W G (William George)

Extractive metallurgy o f copper ~ 4th ed

Library of Congress Cataloging in Publication Data

A catalog record froin the Library of Congress has been applied for

ISBN: 0-08-044029-0

8 The paper used in this publication meets the requirements of ANSL’NISO 239.48-1992 (Permanence of Paper)

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CONTENTS

Preface

Preface to the Third Edition

Preface to the Second Edition

Preface to the First Edition

Extracting Copper from Copper-Iron-Sulfide Ores

Melting and Casting Cathode Copper

Recycle of Copper and Copper-Alloy Scrap

Suggested Reading

References

2 Production and Use

2.1 Locations of Copper Deposits

2.2 Location of Extraction Plants

3.2 Crushing and Grinding (Comminution)

3.3 Flotation Feed Particle S i i -

3.4 Froth Flotation

3.5

3.6 Flotation Cells

3.7 Sensors Operation and Control

Specific Flotation Procedures far Cu Ores

xiii

xv xvii xix

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vi Contents

3.8 The Flotation Product

3.9 Other Flotation Separations

4.2 Matte and Slag

4.3 Reactions During Matte Smelting

4.4

4.5

4.6 Summary

The Smelting Process: General Considerations

Smelting Products: Matte, Slag and Offgas

Suggested Reading

References

5 Flash Smelting - Outokumpu Process

5.1 Outokumpu Flash Furnace

Cu-in-Slag and Molten Converter Slag Recycle

Inco vs Outokumpu Flash Smelting

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Operation and Control

Production Rate Enhancement

9.2 Industrial Peirce-Smith Converting Operations 137

9.5 Recent Developments in Converting- Shrouded Blast Injection 148

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viii Contents

10 Continuous Converting

10 I Common Features of Continuous Converting

10.2 Downward Lance Mitsubishi Continuous Converting

10.3 Solid Matte Outokumpu Flash Converting

10.4 Submerged-Tuyere Noranda Continuous Converting

Decreasing Copper in Slag I: Minimizing Slag Generation

Decreasing Copper in Slag 11: Minimizing Cu Concentration in

The Ideal Direct-to-Copper Process

Industrial Single Furnace Direct-to-Copper Smelting

13.1 The Mitsubishi Process

13.2 Smelting Furnace Details

20 1

20 1

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Electric Slag Cleaning Furnace Details

Converting Furnace Details

Recent Mitsubishi Process Developments

Reaction Mechanisms in Mitsubishi Smelting

Optimum Matte Grade

Impurity Behavior in Mitsubishi SmeltingiConverting

Process Control in Mitsubishi Smelting/Converting

Offgases from Smelting and Converting Processes

Sulfuric Acid Manufacture

Smelter Offgas Treatment

Gas Drying

Acid Plant Chemical Reactions

Industrial Sulfuric Acid Manufacture

Recent and Future Developments in Sulfuric Acid Manufacture

Alternative Sulfur Products

Future Improvements in Sulfur Capture

Industrial Methods of Fire Refining

Chemistry of Fire Refining

Choice of Hydrocarbon for Deoxidation

Casting Anodes

Continuous Anode Casting

New Anodes from Rejects and Anode Scrap

Removal of Impurities During Fire Refining

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Cells and Electrical Connections

Typical Refining Cycle

Refining Objectives

Maximizing Cathode Copper Purity

Optimum Physical Arrangements

Optimum Chemical Arrangements

Optimum Electrical Arrangements

Minimizing Energy Consumption

Recent Developments in Electrorefining

Summary

Suggested Reading

References

17 Hydrometallurgical Copper Extraction:

Introduction and Leaching

17.1 Heap Leaching

17.2 Industrial Heap Leaching

17.3 Steady-State Leaching

17.4 Leaching of Chalcopyrite Concentrates

17.5 Other Leaching Processcs

17.6 Future Developments

17.7 Summary

Suggested Reading

References

18 Solvent Extraction Transfer of Cu

from Leach Solution to Electrolyte

Industrial Solvent Extraction Plants

Quantitative Design of Series Circuit

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Contents xi

19 Electrowinning

19 I Electrowinning Reactions

19.2 Electrowinning Tankhouse Practice

19.3 Maximizing Copper Purity

19.4 Maximizing Current Efficiency

19.5 Future Developments

19.6 Summary

Suggested Reading

References

20 Collection and Processing of Recycled Copper

20.1 The Materials Cycle

The Secondary Copper Smelter

Scrap Processing in Primary Copper Smelters

Overall Investment Costs: Mine through Refinery

Overall Direct Operating Costs: Mine through Refinery

Total Production Costs, Selling Prices, Profitability

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Stoichiometric Data for Copper Extraction

Copper Recovery from Anode Slimes

Sketch of Series-Parallel Solvent Extraction Circuit

Extended List of Chinese Copper Refineries and their

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xx Preface

directed to Metallurgical Thermochemistry by 0 Kubaschewski, E L Evans and

C B Alcock, an earlier volume in this series

The text of the book is followed by four appendixes which contain units and conversion factors: stoichiometric data; enthalpy and free energy data; and a summary of the properties of electrolytic tough pitch copper

Copper is one of man's most beautiful and useful materials It has given us great satisfaction to describe and discuss the methods by which it is obtained Both of

our universities have had a long association with the copper industries of our countries, and it is hoped that, through this book, this association will continue

A K Biswas

University of Queensland

W G Davenport

McGill Universify

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2 Extractive Metallurgy of Copper

Sulfide Ores (0 5 - 2.0% Cu)

-250 ppm oxygen

Continuous casting Fabrication and use

Fig 1.1 Principal processes for extracting copper from sulfide ores Parallel lines

indicate alternative processes *Principally Isasmelt/Ausmelt, reverberatory, shaft, electric, and Vanyukov smelting - Two furnaces, worldwide

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Fabrication and use

Fig 1.2 Hydrometallurgical heap leach copper extraction flowsheet for 'oxide' and chalcocite ores

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4 Extractive Metallurgy of Copper

(a) isolating an ore's Cu-Fe-S (and Cu-S) mineral particles into a concentrate

by froth flotation

(b) smelting this concentrate to molten high-Cu matte

(c) converting the molten matte to impure molten copper

(d) fire- and electrorefining this impure copper to ultra-pure copper

1.2 I Concentration by froth flotation (Chapter 3)

The copper ores being mined in 2002 are too lean in copper (0.5 - 2% Cu) to be smelted directly Heating and melting their huge quantity of waste rock (e.g granite) would require prohibitive amounts of hydrocarbon fuel Fortunately, the Cu-Fe-S and Cu-S minerals in an ore can be isolated by physical means into high-Cu 'concentrate' which can be smelted economically

The most effective method of isolating the Cu minerals is froth flotation This process causes the Cu minerals to become selectively attached to air bubbles rising through a water-finely ground ore mixture, Fig 1.3

Selectivity of flotation is created by using reagents which make Cu minerals water repellent while leaving waste minerals 'wetted' These reagents cause Cu

Air bubble dispersion system

Fig 1.3 Schematic view of flotation cell Reagents cause Cu-Fe sulfide and Cu sulfide minerals in the ore to attach to rising air bubbles, which are then collected in a short-lived

through several cells before being discarded as a final tailing Many types and sizes (up

to 100 m3) of ccll are used, Chapter 3

This froth is de-watered to become concentrate

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Overview 5

minerals to 'float' on rising bubbles while the other minerals remain unfloated The 'floated' Cu-mineral particles overflow the flotation cell in a froth to become concentrate -30% Cu

Flotation is preceded by crushing and grinding copper ore into fines Its use has led to adoption of smelting processes which are effective at treating finely ground material

1.2.2 Matte smelting (Chapter 4)

Matte smelting oxidizes and melts flotation concentrate in a large, hot (1250°C) furnace, Fig 1.1 The objective of the smelting is to oxidize S and Fe from the Cu-Fe-S concentrate to produce a Cu-enriched molten sulfide phase (matte) The oxidant is almost always oxygen-enriched air

Example reactions are:

(1.1)

2CuFeS2 + T O 2 -+ Cu2S.-FeS + -FeO + -SO2

in oxygen molten matte

AH;,,, = - 20 M J k g mole FeO

The products of smelting are (i) molten sulfide matte (45-75% Cu) containing most of the Cu-in-concentrate and (ii) molten oxide slag as free of Cu as possible The molten matte is subsequently converted (oxidized) in a converting furnace to form impure molten copper The slag is treated for Cu recovery then sold or discarded, Chapter 1 1

S02-bearing offgas (10 to 60% SOz) is also generated SO2 is harmful to the environment so it must be removed before the offgas is released to the atmosphere This is almost always done by capturing the SO2 as sulfuric acid, Chapter 14

An important objective of matte smelting is to produce a slag which contains as little Cu as possible This is done by:

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6 Extractive Metallurgy of Copper

*,

Slag

Fig 1.4 Outokumpu oxygen-enriched air flash furnace Flash furnaces are typically 20

m long and 7m wide They smelt 1000 to 3000 tonnes of concentrate per day

Fig 1.5 Noranda submerged tuyere smelting furnace Noranda furnaces are typically 20

to 25 m long and 5 m diameter They smelt 1500 to 3000 tonnes of concentrate per day Teniente smelting furnaces are similar

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