0 -4 cd 1 H 1.0079 Hydrogen Li Be 6.94, Lithium 9.01218 Bervllium 11 12 Na Mg 24.305 E Magnesium 3(IIIA) 19 z4 22.98977 Sodium 20 K 39.098, Pottasium 37 I 6(VIA) 7(VIIA) 9(VIIIA) Nd Pm Sm 144.2, (145) 150.4 Np Pu 25 Cr 40.08 Calcium Manganese 38 Rb 87.62 Strontium 56 cs Ba 132.9054 Cesium 137.33 BariWll 88 42 Y I4'Zr 4Nb Mo Sr 85.467, Rubidium 87 5(VA) Ca 55 4(IVA) 88.9059 Yttrium 91.22 Zirconium 92.9064 95.94 Niobium Molybdenutr kchnetium 57 La 72Hf 73Ta 74W Re 138.9055 Lanthanum 178.4, Hafnium 180.947, Tantalum 183.85 Wolfram 186.207 Rhenium 39 Fr Ra Ac (223) Francium 226.0254 Radium 227.0278 Actinium Lanthanide Metals 90 91 U 238.029 Uranium 237.0482 (244) Nmtunium Plutonium 18 ( I WE He 13 (IIIB) 14 ( N B ) 15(VB) 16(VIB) 17(VIIB) 10.81 10 F Ne 18.998403 Fluorine 12.011 20.17, Neon 17 A1 10 28 11(IB) 12(IIB) 7 i343206 hosphorous Sulphur Zn 31Ga132C;e As Cu 58.70 Nickel 28.085, Silicon 29 Ni 26.98154 Boron 63S6 Copper Se 65.38 Zinc 107.868 Silver 78 79 P% i% 65 Tb i’xm i k m I Bk Xe 131.30 Xenon 86 At Rn (210) (222) Radon Astame 66 67 Dy Ho 158.9254 162.5, 164.9304 Terbium Dysprosium Holmium 97 83.80 Krypton 54 Iodine 200.5, Mercury Gold Br ’“Kr 35 Hg 1%.9665 35 126.9045 80 Au Ar 39.94, Argon I 112.41 Cadmium 1 Pt C1 35.453 Chlorine 53 Pd 47Ag 48Cd 106.4 18 79.904 Bromine 46 palladium 4.00260 Helium 98 99 Cf (247) (251) Berkelium Californium Es (252) ansvlmum 68 Er 167.5 Erbium 100 69 Tm Yb 168.9342 Thulium 101 Fm Md (257) Fermium 70 (258) Mendcirnum 173.0, Ytterbium 02 71 Lu 174.96, Lutetium I03 No Lr 1259) Nobelium (260) Lawrencium Extractive Metallurgy of Copper FOURTH EDITION 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 Extractive Metallurgy of Copper W.G DAVENPORT Department of Materials Science and Engineering University of Arizona Tucson, AZ, USA M KING 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 ELSEVIER SCIENCE Ltd T h e Boulevard, Langford L a n e Kidlington, Oxford OX5 IGB, UK 02002 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 Permissions may be sought directly from Elsevier Science via their homepage (http:l/www.elsevier.com) by selecting ‘Customer support’ and then ‘Permissions’ Alternatively you can send an e-mail to: permissions@elsevier.co.uk, or fax to: (+44) 1865 853333 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 throiigh the Copyright Licensing Agency Rapid Clearance Service (CLARCS), 90 Tottenham Court Road, London WIP OLP, UK: phone: (+44) 207 631 5555; fax: (+44) 207 631 5500 Other countries may have a local reprographic rights agency for payments Derivative Works Tables of contents may be reproduced for internal circulation, but permission of Elsevier Science is required for external resale or distribution of such material Permission of the Publisher is required for all other derivative works, including compilations and translations Electronic Storage or Usage Permission of the Publisher is required to store or use electronically any material contained in this work, including any chapter or part of a chapter Except as outlined above, no part of this work may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without prior written permission of the Publisher Address permissions requests to: Elsevier Science Global Rights Department, at the fax and e-mail addresses noted above 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 Second edition Third edition Fourth edition 1916 1980 1994 2002 British Library Cataloguing in Publication Data Davenport, W G (William George) Extractive metallurgy of copper 4th ed 1.Copper - Metallurgy 1.Title II.King, M III.Schlesinger, M IV.Biswas, A K (Ani1 Kumar) 669.3 ~ ISBN 0080440290 Library of Congress Cataloging in Publication Data A catalog record froin the Library of Congress has been applied for ISBN: 0-08-044029-0 The paper used in this publication meets the requirements of ANSL’NISO 239.48-1992 (Permanence of Paper) Printed in The Netherlands CONTENTS xiii xv xvii xix Preface Preface to the Third Edition Preface to the Second Edition Preface to the First Edition 1 I 1.2 1.3 1.4 I 1.6 Introduction Extracting Copper from Copper-Iron-Sulfide Ores Hydrometallurgical Extraction of Copper Melting and Casting Cathode Copper Recycle of Copper and Copper-Alloy Scrap Summary Suggested Reading References Locations of Copper Deposits Location of Extraction Plants Copper Minerals and ‘Cut-Off Grades Price of Copper Summary References Concentrating Copper Ores 3.1 3.2 3.3 3.4 3.5 3.6 3.7 1 11 13 15 15 16 16 17 Production and Use 2.1 2.2 2.3 2.4 2.5 Overview Concentration Flowsheet Crushing and Grinding (Comminution) Flotation Feed Particle SiiFroth Flotation Specific Flotation Procedures far Cu Ores Flotation Cells Sensors Operation and Control V 18 18 19 28 29 29 31 31 33 38 42 46 49 50 vi Contents 3.8 3.9 3.10 Matte Smelting Fundamentals 4.1 4.2 4.3 4.4 4.5 4.6 Why Smelting? Matte and Slag Reactions During Matte Smelting The Smelting Process: General Considerations Smelting Products: Matte, Slag and Offgas Summary Suggested Reading References Flash Smelting - Outokumpu Process 5.1 5.2 5.3 5.4 5.5 5.6 5.7 The Flotation Product Other Flotation Separations Summary Suggested Reading References Outokumpu Flash Furnace Peripheral Equipment Furnace Operation Control Impurity Behavior Future Trends Summary Suggested Reading References 52 53 53 54 54 57 57 59 65 66 67 70 70 70 73 74 77 82 83 86 87 87 88 88 Inco Flash Smelting 91 6.1 6.2 6.3 91 96 97 98 100 6.4 6.5 6.6 6.7 Furnace Details Auxiliary Equipment Operation Control Strategy Cu-in-Slag and Molten Converter Slag Recycle Inco vs Outokumpu Flash Smelting Summary Suggested Reading References 101 101 101 102 Contents Noranda and Teniente Smelting 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 7.10 7.1 I 7.12 7.13 103 Noranda Process Reaction Mechanisms Operation and Control Production Rate Enhancement Noranda Future Teniente Smelting Process Description Operation Control Impurity Distribution Teniente Future Discussion Summary Suggested Reading References 104 106 108 109 1I O 1I O 111 111 I3 I4 115 115 I6 I7 I7 Ausmeltflsasmelt Matte Smelting 119 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 vii Basic Operations Feed Materials The Isasmelt Furnace and Lance Smelting Mechanisms Startup and Shutdown Current Installations Other Coppermaking Uses of AusmeltiIsasmelt Technology Summary Suggested Reading References Batch Converting of Cu Matte 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Chemistry Industrial Peirce-Smith Converting Operations Oxygen Enrichment of Peirce-Smith Converter Blast Maximizing Converter Productivity Recent Developments in Converting- Shrouded Blast Injection Alternatives to Peirce-Smith Converting Summary Suggested Reading References 119 120 120 125 126 126 127 127 128 129 131 131 137 144 145 148 148 150 151 151 viii Contents 10 Continuous Converting 10.I 10.2 10.3 10.4 10.5 10.6 11 Copper Loss in Slag 1.1 I 1.2 11.3 1.4 I 1.5 11.6 12 Copper in Slags Decreasing Copper in Slag I: Minimizing Slag Generation Decreasing Copper in Slag 11: Minimizing Cu Concentration in Slag Decreasing Copper in Slag 111: Pyrometallurgical Slag Settling/Reduction Decreasing Copper in Slag IV: Slag Minerals Processing Summary Suggested Reading References Direct-To-Copper Flash Smelting 12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13 Common Features of Continuous Converting Downward Lance Mitsubishi Continuous Converting Solid Matte Outokumpu Flash Converting Submerged-Tuyere Noranda Continuous Converting % Cu-in-Slag Summary Suggested Reading References The Ideal Direct-to-Copper Process Industrial Single Furnace Direct-to-Copper Smelting Chemistry Industrial Details Control Cu-in-Slag: Comparison with Conventional Matte SmeltingiConverting Cu-in-Slag Limitation of Direct-to-Copper Smelting Direct-to-Copper Impurities Summary Suggested Reading References Mitsubishi Continuous SmeltingKonverting 13.1 13.2 The Mitsubishi Process Smelting Furnace Details 155 155 157 162 166 170 170 171 171 173 173 175 176 176 181 181 183 183 187 187 188 189 190 190 193 194 195 195 196 196 199 20 20 Contents 13.3 13.4 13.5 13.6 13.7 13.8 13.9 13.10 14 Capture and Fixation of Sulfur 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 14.10 15 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 Summary Suggested Reading References Fire Refining and Casting of Anodes: Sulfur and Oxygen Removal 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 16 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 Summary Suggested Reading References 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 Summary Suggested Reading References Electrolytic Refining 16.1 Principles ix 203 203 207 208 210 210 21 212 214 215 217 217 218 222 224 227 23 240 24 24 242 243 243 247 247 252 253 253 256 260 260 26 26 262 265 265 x Contents 16.2 16.3 16.4 16.5 16.6 16.7 16.8 16.9 16.10 16.11 16.12 16.13 16.14 16.15 17 269 272 273 273 278 279 280 280 280 28 282 283 283 284 284 285 Hydrometallurgical Copper Extraction: Introduction and Leaching 289 Heap Leaching Industrial Heap Leaching Steady-State Leaching Leaching of Chalcopyrite Concentrates Other Leaching Processcs Future Developments Summary Suggested Reading References 289 293 299 300 301 301 30 303 303 17.1 17.2 17.3 17.4 17.5 17.6 17.7 18 Behavior of Anode Impurities During Electrorefining Industrial Electrorefining Cathodes Electrolyte 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 Solvent Extraction Transfer of Cu from Leach Solution to Electrolyte 18.1 18.2 18.3 18.4 18.5 18.6 18.7 18.8 The Solvent Extraction Process Chemistry Extractants Industrial Solvent Extraction Plants Quantitative Design of Series Circuit Stability of Operation 'Crud' Summary Suggested Reading References 307 307 309 310 312 317 32 322 323 324 324 Contents 19 Electrowinning 19.I 19.2 19.3 19.4 19.5 19.6 20 Collection and Processing of Recycled Copper 20.1 20.2 20.3 20.4 21 328 329 335 335 337 337 338 338 341 341 344 346 351 35 352 Chemical Metallurgy of Copper Recycling 355 The Secondary Copper Smelter Scrap Processing in Primary Copper Smelters Summary Suggested Reading References Melting and Casting 22 I 22.2 22.3 22.4 23 327 The Materials Cycle Secondary Copper Grades and Definitions Scrap Processing and Beneficiation Summary Suggested Reading References 1.1 I 21.3 22 Electrowinning Reactions Electrowinning Tankhouse Practice Maximizing Copper Purity Maximizing Current Efficiency Future Developments Summary Suggested Reading References xi Product Grades and Quality Melting Technology Casting Machines Summary Suggested Reading References Costs of Copper Production 23.1 23.2 23.3 Overall Investment Costs: Mine through Refinery Overall Direct Operating Costs: Mine through Refinery Total Production Costs, Selling Prices, Profitability 355 360 363 363 364 367 361 370 374 380 38 381 385 386 389 389 xii Contents 23.4 23.5 23.6 23.7 23.8 23.9 23.10 Concentrating Costs Smelting Costs Electrorefining Costs Production of Copper from Scrap Leach/Solvent Extraction/Electrowinning Costs Profitability Summary References Appendices A B C D E Index Stoichiometric Data for Copper Extraction Lesser-Used Smelting Processes Copper Recovery from Anode Slimes Sketch of Series-Parallel Solvent Extraction Circuit Extended List of Chinese Copper Refineries and their Capacities 391 393 395 397 397 398 399 399 401 40 403 413 415 416 417 xx Preface directed to Metallurgical Thermochemistry by 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 Extractive Metallurgy of Copper Sulfide Ores (0 - 2.0% Cu) Comminution Flotation I Concentrates (20 - 30% Cu) Matte (5d-70°/&u) Multl-furnace continuous coppermaking Converting Anode refining and casting v I + Anodes (99.5% Cu) Electrorefining + c ] fi Cathodes Melting Molten copper,