Handbook of Extractive Metallurgy Edited by Fathi Habashi Volume II: Primary Metals Secondary Metals Light Metals GQ WILEY-VCH Weinheim· Chichester·NewYork·Toronto· Brisbane·Singapore ProfessorFathiHabashi UniversiteLaval DepartementdeMinesetdeMetallurgie Preface QuebecG1K7P4 Canada Extractivemetallurgyis thatbranchofmet presentfourvolumeswillfillthe gapformod allurgythatdealswithoresasrawmaterialand ernextractivemetallurgy. Thisbookwas carefullyproduced.Nevertbeles,theeditor,the autors andpublisherdonotwarrantthe metals asfmishedproducts. Itis·an ancientart TheHandbook is an updated collection of informationcontainedthereintobefreeoferrors.Readersareadvisedtokeepinmindthatstatements, that has been transformed into a II;lodern sci more than ahundredentries in UllmannsEn data,illustrations,proceduraldetailsorotheritemsmayinadvertentlybeinaccurate. ence as aresult ofdevelopments inchemistry cyclopediaofIndustrialChemistlYwrittenby andchemicalengineering.Thepresentvolume over200 specialists. Some articles were writ is acollectiveworkofanumberofauthors in tenspecificallyfortheHandbook. Someprob which metals, theirhistory, properties, extrac lems are certainly faced when preparing such EditorialDirectors:KarinSora,llseBedrich tiontechnology, andmost importantinorganic avastamountofmaterial. Thefollowingmay ProductionManager:PeterJ.Biel compounds and toxicology are systematically bementioned: CoverIllustration:MichelMeyer/mmad described. • Although arsenic, antimony, bismuth, bo Metals are neitherarranged by alphabetical ron, germanium, silicon, selenium, and tel order as in an encyclopedia, nor according to lurium are metalloids because they have the Periodic Table as in chemistry textbooks. covalentandnotmetallicbonds,they arein The system used here is according to an eco cluded here because most ofthem are pro nomic classification which reflects mainly the duced in metallurgical plants, either in the LibraryofCongressCardNo.appliedfor uses,theoccurrence,andtheeconomicvalueof elementalformorasferroalloys. A CIPcataloguerecordforthisbookisavailablefromtheBritishLibrary metals. First, the ferrous metals, i.e., the pro duction ofiron, steel, and ferroalloys are out • Each chapter contains the articles on the metalinquestionanditsmostimportantinor lined. TheIL nonferrous metals are subdivided ganiccompounds.However, therearecertain intoprimarY, secondary, light, precious,refrnc compounds that are conveniently described tory,scattered,radioactive, rareearths,ferroai togetherandnotunderthemetalsinquestion loy metals, the alkali, and the alkaline earth metals. for a variety of reasons. These are: the hy drides, carbides, nitrides, cyano compounds, Although the general tendency today in DieDeutscheBibliothek- CIP-Einheitsaufnahme peroxocompounds,nitrates,nitrites,silicates, HandbookofextractivemetallurgyIed.byFathiHabashi. teachingextractivemetallurgy is basedonthe fluorine compounds, bromides, iodides, Weinheirn;NewYork;Chichester;Brisbane;Singapore;Toronto: fundamental aspects rather than on a system sulfites, thiosulfates, dithionites, and phos WILEY-VCH ISBN3-527-28792-2 aticdescription ofmetalextractionprocesses, phates. Theseare collectedtogetherinaspe Vol.1.Themetalindustry,ferrousmetals.-1997 it has been found by experience that the two cialsupplemententitledSpecialTopics,under Vol.2.Primarymetals,secondarymetals,lightmetals.-1997 approaches are complementary. The student preparation. musthaveabasicknowledge ofmetalextrac Vol.3.Preciousmetals,refractorymetals,scatteredmetals,radioactivemetals,rareearthmetals.-1997 tion processes: hydro-, pyro-, and electromet • Becauseoflimitationofspace,itwasnotpos Vol.4.Ferroalloymetals,alkalimetals,alkalineearthmetals;Nameindex;Subjectindex.-1997 allurgy, and at the same time he must have at sible to include the alloys of metals in the his disposal a description ofhow aparticular present work. Another supplement entitled ©VCHVerlagsgesellschaftmbH- AWileycompany, metal is extracted industrially from different Alloysisunderpreparation. D-69451Weinheim,FederalRepublicofGermany,1997 rawmaterialsandknowwhatareitsimportant • Since the largest amount of coke is con Printedonacid-freeandlow-chlorinepaper compounds. It is for this reason, that this sumed in iron production as compared to All rights reserved (including those of translation into other languages). No part ?f this book may. be Handbookhasbeenconceived. other metals, the articles "Coal" and "Coal reproducedinanyform- byphotoprinting,microfilm,oranyothermeans- nortransIDlttedortranslatedmto TheHandbookisthefirstofitstypeforex Pyrolysis" are includedin the chapterdeal amachinelanguagewithoutwrittenpermissionfromthepublishers.Registerednames,trademarks,etc.usedin thisbook,evenwhennotspecificallymarkedassuch,arenottobeconsideredunprotectedbylaw. tractive metallurgy. Chemical engineers have ingwithiron. Composition:JeanFran~oisMorin,Quebec,Canada already hadtheirPerry'sChemicalEngineers' IamgratefultotheeditorsatVCHVedags Printing:StraussOffsetdruckGmbH,D-69509Morlenbach Handbook for over fifty years, and physical gesellschaftfortheirexcellent cooperation, in Bookbinding:WIlhelmOswald&Co.,D-67433NeustadtlWeinstraBe metallurgists have an impressive 18-volume particularMrs. Karin Sora who followed the PrintedintheFederalRepublicofGermany ASMMetals Handbook. It is hoped that the project since its conception in 1994, and to vi HandbookofExtractiveMetallllrgy Jean-Fran<;:ois Morin at LavalUniversity for thereforebeusefultoindustrialchemistsaswell. Table ofContents hisexpertiseinwordprocessing. Itcanalso beuseful to engineers andscientists Thepresentworkshouldbeusefulasarefer from otherdisciplines, butitis an essential aid ence workfor the practising engineers and the fortheextractivemetallurgist. students ofmetallurgy, chemistry, chemicalen volumeI Part Refractory Metals gineering, geology, mining, andmineralbenefi Seven 26 Tungsten 1329 Part One The Metal Industry ciation. Ei'l.1ractivemetallurgy andthe chemical 27 Molybdenum 1361 induslIy are closelyrelated; thisHandbookwill FarMHabashi 1 TheEconomic Classifica- 28 Niobium 1403 tionofMetals.. : ~ 1 29 Tantalum ~..1417 2 MetalProduction 15 30 Zirconium 1431 3 RecyclingofMetals 21 31 Hafnium 1459 4 By-ProductMetals 23 32 Vanadium 1471 Part Two Ferrous Metals .33 Rhenium 1491 5 Iron 29 PartEight Scattered Metals 6 Steel 269 7 Ferroalloys 403 34 Germanium 1505 35 Gallium 1523 Volume II 36 Indium 1531 37 Thallium 1543 Part Primary Metals 38 Selenium 1557 Three 8 Copper 491 39 Tellurium 1571 9 Lead 581 PartNine Radioactive Metals 10 Zinc 641 II Tin 6g3 40 General. 1585 12 Nickel 715 41 Uranium 1599 42 Thorium 1649 PartFour SecondaryMetals 43 Plutonium 1685 13 Arsenic 795 14 Antimony 823 Part Ten Rare Earth Metals 15 Bismuth 845 44 General. 1695 16 Cadmium 869 45 Cerium 1743 17 Mercury 891 18 Cobalt 923 volumeIV PartFive LightMetals Part Ferroalloy Metals 19 Beryllium 955 Eleven 46 Chromium 1761 20 Magnesium 981 47 Manganese 1813 21 Aluminum 1039 48 Silicon 1861 22 Titanium 1129 49 Boron 1985 ~'olume III Part Alkali Metals PartSix Precious Metals Twelve 50 Lithium 2029 23 Gold 1183 51 Sodium 2053 24 Silver. 1215 52 Potassium 2141 25 PlatinumGroup 53 Rubidium 2211 Metals 1269 54 Cesium 2215 viii HandbaakafExtractiveMetallllrgy Part Three 55 Alkali Sulfur Compounds 2221 Primary Metals Part Alkaline Earth Metals Thirteen 56 Calcium 2249 57 Strontium 2329 58 Barium 2337 H "He ~u~ors 2355 Name Index 2375 . Li Be B C N 0 F Ne SubjectIndex 2379 Na Mg AI Si P S CI AI K Ca Sc Ii V Cr Mn Fe Co As Se Br Kr Rb Sr Y Zr Nb Mo Ie Ru Rh Sb Ie I Xe Cs Ba Lat Hf Ia W Re Os Ir Bi Po At Rn Fr Ra Act 8 Copper HARALDFABIAN t (§§ 8.1-8.10); HUGH WAYNERiCHARDSON (§ 8.11 EXCEPT8.11.3.4);FATIll HABASIll (§ 8.11.3.4); ROBERTBESOLD(§8.12) 8.1 Introduction..................... 492 8.6.1.2 ContinuousFireRefining......... 531 8.2 PhysicalProperties '.'..',' 493 8.6.1.3 CastingofAnodes 531 8.6.2 Electrolytic ~ 531 8.3 ChemicalProperties.............. 495 8.6.2.1 Principles..................... 532 8.4 Occurrence...................... 497 8.6.2.2 Practice...................... 534 8.4.1 CopperMinerals............... 497 8.6.3 MeltingandCasting. ............ 536 .8.4.2 OriginofCopperOres........... 498 8.6.3.1 RemeltingofCathodes , 536 8.4.3 CopperOreDeposits '.'.......... 499 8.6.3.2 DiscontinuousCasting. .......... 536 8.4.4 CopperResources .............. 500 8.6.3.3 ContinuousCasting ............. 536 8.4.5 Mining....................... 500 8.6.3.4 ContinuousRodCastingandRolling 537 8.5 Production....................... 501 8.6.4 CopperPowder................. 538 8.5.1 Beneficiation.................. 501 8.6.5 CopperGradesandStandardization. 539 8.5.2 Segregation................... 503 8.6.6 QualityControlandAnalysis...... 540 8.5.3 Roasting 503 8.7 Processing 541 8.5.4 PyrometallurgicalPrinciples...... 505 8.7.1 WorkingProcesses 541 8.5.4.1 BehavioroftheComponents 505 8.7.2 OtherFabricatingMethods........ 541 8.5.4.2 Matte........................ 505 8.7.3 Uses 542 8.5.4.3 Slags........................ 506 8.8 EconomicAspects 543 8.5.4.4 OxidizingSmeltingProcesses..... 507 8.5.4.5 Proposals..................... 509 8.9 EnvironmentalProtection 545 8.5.5 TraditionalBathSmelting........ 510 8.10 Toxicology 546 8.5.5.1 BlastFurnaceSmelting.......... 510 8.11 Compounds...................... 546 8.5.5.2 ReverberatoryFurnaceSmelting... 510 8.1Ll TheCopperIons................ 547 8.5.5.3 ModemReverberatorySmelting... 512 8.11.2 BasicCopperCompounds 548 8.5.5.4 ElectricFurnaceSmelting. ....... 512 8.11.2.1- Copper(1)Oxide 548 8.5.6 AutogenousSmelting ........... 513 8.11.2.2 Copper(ll)Oxide " 549 8.5.6.1 OutokumpuFlashSmelting....... 514 8.11.2.3 Copper(ll)Hydroxide 550 8.5.6.2 INCOFlashSmelting. ........... 515 8.11.2.4 Copper(ll)CarbonateHydroxide 552 8.5.6.3 KIVCETCycloneSmelting....... 516 8.11.3 SaltsandBasicSalts............. 553 8.5.6.4 FlameCycloneSmelting. ........ 517 8.11.3.1 Copper(1)Chloride 553 8.5.7 Converting.................... 518 8.11.3.2 Copper(ll)Chloride 555 8.5.7.1 DiscontinuousConverting. ....... 518 8.11.3.3 Copper(II)Oxychloride 556 8.5.7.2 ContinuousConverting.......... 521 8.11.3.4 Copper(I)Sulfate............... 557 8.5.8 ContinuousSmeltingandConverting521 8.11.3.5 Copper(II)Sulfates. ............. 557 8.5.8.1 MitsubishiProcess.............. 521 8.11.4 CompoundsandComplexesofMinor 8.5.8.2 NorandaProcess............... 522 Importance.................... 563 8.5.8.3 OtherProcesses................ 523 8.11.4.1 Compounds 563 8.5.9 RecoveryofCopperfromSecondary 8.11.4.2 Complexes 567 Materials ..................... 524 8.11.5 Reclamation................... 568 8.5.10 HydrometallurgicalExtraction.... 525 8.11.6 CopperandtheEnvironment 569 8.5.10.1 Principles..................... 526 8.11.7 EconomicAspects 570 8.5.10.2 Processes.................. 528 8.11.8 ToxicologyandOccupationalHealth 571 8.6 Refming 529 8.12 CopperPigments................. 571 8.6.1 Pyrometallurgical............... 529 8.6.1.1 DiscontinuousFireRefining...... 529 8.13 .References....................... 572 492 HandbookofExtractiveMetal/urgy Copper 493 8.1 Introduction oldest. In the Old World, copper has been Independent ofthe OldWorld, the Indians Table 8.1: World mine production ofcopper (approxi mate,fromseveralsources). workedandusedsinceapproximately: of North America had formed utensils by Copper, the red metal, apartfrom gold the 7000B.C. Anatolia working nativecopperlongbeforethetime of Year ProdlOuJcttion, Year ProdlOuJcttion, 4000B.C. Egypt,Mesopotamia,Palestine,Iran,and Christ, although the skills of smelting and only metallic element with a color different Turkestan casting were unknown to them. On the other 1700 9 1960 4200 from a gray tone, has been known since the 3000B.C. Aegean,India hand,theskillofcoppercastingwasknownin 11880500 5177 11996750 56040000 early days of the human race. It has always 2600B.C. Cyprus Peruca. 500A.D., andinthe 15thcenturythe 1900 450 1975 7300 been one of the significant materials, and to 2500B.C. Iberia,Transcaucasis,andChina 1950 2500 1980 7900 day itis the mostfrequently used heavy non 2200B.C. CentralEurope Incasknew howtowinthe metalfrom sulfide 1955 3100 1984 8100 2000B.C. BritishIsles ores. ferrous metal. The utility of pure copper is 1500B.C. Scandinavia Around 1500, Germany was'the"world basedonitsphysical and chemicalproperties, 8.2 PhysicalProperties Empirical experience over millennia has leader in copper production, and the Fugger above all, itselectricalandthermalconductiv led to an astonishing knowledge of copper family dominated world copper trade. By ity (exceeded only by silver), its outstanding Mostproperties ofmetallic copperdepend on metallurgicaloperations: 18"00,Englandhad gainedfirstplace,process ductility and thus excellent workability, and the degree ofpurity and on the source of the • Native copperwas hardened byhammering ingoresfromherownsourcesandforeignpits its corrosion resistance (a chemical behavior metal.Variationsinpropertiesarecausedby: (cold working) and softened by moderate into metal. Near 1850,Chilebecamethemost makingitahalf-noblemetal). • Grade of copper, i.e., the oxygen content: heating(annealing). importantproducerofcopperores,andtoward Its common alloys, particularly brass and the end ofthe last century, the United States tough-pitch, deoxidized copper, oxygen bronze,areofgreatpracticalimportance.Cop • Heating to higher temperatures (charcoal hadtakentheworldleadinminingcopperores freecopper and bellows) produced molten copper and per compounds ores are distinguished by andinproductionofrefmedcopper. • Content of native impurities (e.g., arsenic) made possible the founding into forms of brightcoloration, especially reds, greens, and Technicaldevelopmentinthecopperindus orremnants ofadditives (e.g., phosphorus), stone,clay,andlatermetal. blues. Copperin soil is an essentialtrace ele tryhasmadeenormousprogressinthelast120 which form solid solutions or separate mentformostcreatures,includinghumans. • Similar treatmentofthe conspicuously col years. The blast furnace, based on the oldest phasesatthegrainboundaries ored oxidized copper ores formed copper Etymology.Accordingtomythology,thegod principle of copper production, was continu • Thermalandmechanicalpretreatmentofthe metal. ally developed into moreefficientunits. Nev metal, whichleadtostates such as castcop dess Venus (or Aphrodite) was born on the • The treatment ofsulfide copper ores (chal ertheless, after World War I, it was per, hot-rolled copper, cold-worked (hard) Mediterranean island of Cyprus, formerly copyrite), however, did notresultin copper increasinglyreplacedbythereverberatoryffir copper, annealed(soft) copper, and sintered Kurrpoc;(Greek), wherecopperwasexploited millennia before Christ. Therefore, in early metal, butin coppermatte (a sulfidic inter nace, first constructed in the United States. copper times the Romans named it cyprium, later mediate). Not before 2000 B.C. did people SincetheendofWorldWarn,thisfurnacehas These property differences are caused by the calledcuprum.Thisnameistheoriginofcop succeedinconvertingthe matteinto copper been superseded slowly by the flash smelting detects in the crystal lattice. Two groups of per and of the corresponding words in most byrepeatedroastingandsmelting. furnace inventedin Finland.Recently, several propertiesaretobedistinguished: RomanceandGermaniclanguages,e.g.,cobre • In early times, bronze (copper-tin alloy) even more modern methods, especially from • Low dependence on crystal lattice detects, (Spanish and Portuguese), cuivre (French), was won from complex ores, the Bronze Canada and Japan; have begun to compete e.g., caloric and thermodynamic properties, Kupfer (German), koper (Dutch), and koppar Age beginning ca. 2800 B.C. Atfirst, cop withtheolderprocesses. magnetic behavior, and nuclearcharacteris (Swedish). per ores were smelted with tin ores; later, An important development in producing tics bronze was produced from metallic copper crude metal was the application oftheBesse A "cross with handle", from the Egyptian • High dependenceon defects, e.g., electrical and tin. Brass (copper-zinc alloy) was mer converter concept to copper metallurgy epoch, was called the mirror ofVenus. In the and thermal conductivity, plastic behavior, known ca. 1000 B.c. and became widely by Manhes and David (France, 1880): this alchemistic period, this sign meant the metal kinetic phenomena, andresistanceto corro usedintheeraoftheRomanEmpire. principleis stillthe mostwidely usedmethod copper. Even now in astronomy it designates sion In Roman times, most copper are was forcopperconvertingintheworld. theplanetVenusandinbiology standsfor ''fe The variations in properties are caused ei mined in Spain (Rio Tinto) and Cyprus. With Over time the requirements for copper pu male". therbyphysicallatticeimperfections(disloca the fall of the Roman Empire, mining in Eu rity have become increasingly stringent. The tions, lattice voids, and interstitial atoms) or History [21-24]. The first metals found by rope came to avirtual halt. InGermany (Sax invention and development ofelectrolysis by by chemical imperfections (substitutional Neolithic man weregold and copper, latersil ony),miningactivitieswere notresumeduntil J.B.Elkington (England, 1865) andE. Wohl solidsolutions). verandmeteoric iron.Theearliestfindings of 920A.D.DuringtheMiddleAges,miningand will (Germany, 1876) made refming of high copperarepresumedtobenearly ninemillen winning of metals expanded from Germany puritycopperpossible. Atomicand NuclearProperties.The atomic niaoldand camefrom theregion near Konya over the rest ofEurope. In the middle ofthe In addition, the quantity of copper pro number of copperis 29, and the atomic mass in southern Anatolia (Turkey). Until recently 16thcentury,the currentknowledge ofmetals duced has increased immensely (Table 8.1). A, is 63.546 ± 0.003 (IUPAC, 1983). COfler the six-millennia-old copper implements was compiledinadetailedpublication [23] by Since 1880, ca. 275 X 106 t was mined be consists of two natural isotopes, Cu fromIran(TeleSialk)werepresumedtobethe GeorgiusAgricola,DeReMetallica(1556). tween 1800and 1900. (68.94%) and 65Cu (31.06%). There are also 494 HandbookofExtractiveMetallurgy Copper. 495 nine synthetic radioactive isotopes with quent annealing eliminates the hardening and conductivity of copper is the highest of all ments thatform oxidic compounds that sepa atomic masses between 59 and 68, of which strengtheningsothattheoriginalsoftstatecan metalsexceptsilver. rate at grain boundaries affect electrical propertiesonlyslightly.Coppermayloseupto 67Cuhas thelongesthalf-life,ca.58.5h. bereproduced(softcopper).Theworkingpro Table8.3:Thermalpropertiesofcopper. ca. 3% of its conductivity by cold working; cesses are based on this behavior. Impurities Crystal Structure. At moderate pressures, Property Unit Value however, subsequent annealing restores the that form solid solutions ofthe substitutional copper crystallizes from low temperatures up Meltingpoint K 1356(1083DC) original value. There is a simple rule: the to· its melting point in a cubic-closest-packed type likewise increase hardness and tensile Boilingpoint K 2868(2595DC) (ccp) lattice, typeAl (alsoFI orCu) with the strength. Heatoffusion JIg 210 harderthecopper,thelowerisitsconductivity. coordinationnumber 12.X-ray structure anal Table8.2:Mechanicalpropertiesofcopperatroomtem HVaepaotropfrveaspsourrieza(atitomnp) JPIga 04.801703 OtherProperties. High-purity copper is dia 2ys0i°sC)y:ields the following dimensions (at perature. Annealed Cold-worked Satp2ec9i3ficKh(e2a0tDcaCp)aciry xma1g0n-6etcicmw3/githataromoamsstesumspceerpattiubrilei.tyTho~f-d0e.p0e8n5 Property Unit (soft) (hard) and100kPa(1bar) Jg-l~l 0.385 dence on temperature is small. However, a Latticeconstant 0.36152run MAtionmimicurmadiinutseratomicdistance 00..21525716nrurnn Elasticmodules GPa 1c0o0p--p1e2r0 1c2o0p--p1e3r0 ata1n2d3100K0k(9P5a7DC) 0.494 mveargynleotwiccpornotpeenrttioefsiorofncocpanpesrt.ronglyaffectthe Atomicvolume 7.114cm3/mol Shearingmodulus GPa 40--45 45-50 Averagespecificheat Thelowerthefrequency oflight,thehigher Poisson'sratio 0.35 273--573K(0--300DC) Density.· The theoretical density at 20°C, Tensilestrength MPa 200--250 300--360 at100kPa(1bar) Jg-1K-1 0.411 thereflectivityofcopper.Thecolorofaclean, computed from lattice constant and atomic Yieldstrength MPa 40--120 250--320 273--1273K(0--1000DC) solidsurfaceofhigh-puritycopperistypically 3 Elongation % 30--40 3--5 at100kPa 0.437 massis 8.93 g/cm .Theinternationalstandard salmonred. 3 Brinellhardness (HE) 40--50 80--110 Coefficientoflinearthermal was fIxed at 8.89 g/cm in 1913 by the IEC Vickershardness (HV) 45-55 90--120 expansion The surface tension of molten copper is (International Electrotechnical Commission). Scratchhardness =3 273--373K(0--100DC) ~l 16.9X 10-6 11.25 X 10-3 N/cm at 1150°C, and the dy The maximum value for 99.999% copper 273--673K(0--400DC) 17.9x10-6 namicviscosity is 3.5 x 10-3Pa·s at 1100DC. Pure copper has outstanding hot workabil between273and1173K reaches nearly8.96g/cm3. ity without hot brittleness, but the high-tem (0--900DC) 19.8x10-6 Detailed physical-property information and Thedensity ofcommercial copperdepends perature strength is low. Detrimental Thermalconductivity data are to be found in the literature, particu onitscomposition,especiallytheoxygencon at293K(20DC) Wm-1K-1 394 larlyas tabularcompilations [25-30]. impurities, those that decrease the strength at tent, its mechanical and thermalpretreatment, high temperatures, are principally lead, bis Electrical properties. In practice, the most Table8.4:Temperaturedependenceofthermalandelec andthetemperature.At20°C,awiderangeof tricalconductivityofcopper. muth, antimony, selenium, tellurium, and sul important property ofcopper is its high elec valuesarefound: fur. The concentration of oxides of such trical conductivity; among all metals only sil Temperature Thermal Electrical CCoasldt-towuogrhk-epditacnhdealencnteroalleydticcocpoppeprer 88..3809---88..9730gg11ccmm33 elements at the grain boundaries during heat ver is a better conductor. Both electrical K DC conWdmuc-t1ivKity, conMduScltmivity, Castoxygen-freeelectrolyticcopper 8.85-8.93g1cm3 ing causes the embrittlement. However, such conductivity and thermal conductivity are 17 -256 5000 The values for cold-worked copper are an effectcanbedesirablewhenfree cuttingis connected with the Wiedemann-Franz rela 73 -200 574 460 higherthan thoseofcastingsbecausethe cast required. Atsubzerotemperatures,copperis a tion andshow strongdependenceontempera 113 -160 450 ingshavepores andgascavities. high-strength material without cold brittle ture (Table 8.4). The old American standard, 217733 -1000 433958 16100 The density of copper is nearly a linear ness. 100% IACS (International Annealed Copper 293 20 394 58 function of temperature, with a discontinuity The changes in typical mechanical proper Standard), corresponds to 58.0 MS/m at 373 100 385 44 atthemeltingpoint: ties such as tensile strength, elongation, and 20°C, anditisstillwidely used in theUnited 457733 230000 338717 3274 t,DC hardness byheattreatmentresultfrom recrys States.Thecorrespondingelectricalresistivity 973 700 338 15 tallization[25].Thedependenceofrecrystalli (p) is 1.7241 x 10--8Q·cm, and the less usual solidcopper:20 8.93 600 8.68 zation temperature and grain size on the resistivity based on weight (density of 8.89 8.3 ChemicalProperties 900 8.47 duration of heating the amount of previous g/cm3, IEC) is 0.1533 W·gm-l. The corre 1083 8.32 cold deformation and the degree ofpurity of sponding temperature coefficients are 0.0068 Intheperiodictable,copperisplacedinpe liquidcopper:1083 7.99 coppercanbedeterminedfrom diagrams. The X 10--8 QmK-I (dp/d1) and 0.00393 K-l (p-l riod 4 and subgroup IB (together with silver 1200 7.81 recrystallization temperatureis ca. 140°Cfor dp/d1). The theoretical conductivity at 20°C and gold); therefore, it behaves as a typical ThesolidifIcationshrinkageis4%;thespe high-purity copper and is 200--300°C for isnearly60.0MS/mor103.4%IACS, andto transitionmetal. Itappears inoxidation states 3 cificvolumeat20°Cis0.112cm /g. common types ofcopper.A low recrystalliza day commercial oxygen-free copper (e.g. +1 to +4, its compounds are colored, and it Mechanical Properties. Important mechani tion temperature is usually advantageous, but C10200 or Cu-OF) has a conductivity of tendstoformcomplexions. cal values are given in Table 8.2. High-purity highervaluesarerequiredtomaintainstrength 101%IACS. Atrelatively low temperature, copper(II)is copper is an extremely ductile metal. Cold andhardnessifthemetalisheatedduringuse. The factors that increase the strength de the most stable state, but above 800°C, cop working increases the hardness and tensile Thennal Properties. Important thermal val crease electrical conductivity: cold working per(I) predominates, which is signifIcant for strength(hardorhard-workedcopper); subse- ues are compiled in Table 8.3. The thermal and elements that form solid solutions. Ele- pyrometallurgical processes; oxidation states :..:+"~ ~ 496 HandbookofExtractiveMetallurgy Copper 497 , i +3 and +4 were discovered in recent years in Therefore, copper is essentially not at graphs give aroughindicationofthefeasibil Nitrogen,carbonmonoxide, andcarbondi \ somecoordinationcompounds. tacked by nonoxidizing acids, such as dilute ity of electrochemical reactions. Figure 8.1 oxide are practically insoluble in liquid or The distribution of the 29 electrons is Is2 sulfuric, hydrochloric, phosphoric, or acetic shows thebehaviorofcopperatroomtemper solid copper. Hydrocarbons generally do not 2s22p63s23p63d104sl. Fromthis electron con andotherorganicacids. ature and atmospheric pressure. The Cu-H20 react with copper. An exception. acetylene 10 figuration, [Ar]3d 4sl, is derived the cop Dissolution ofcopper is possible either by system contains·three fields ofdifferent char (ethyne), reacts at room temperature to form per(I) ion (Cu+) with a complete M shell (18 oxidation or by formation ofcomplexed cop acter: electrons). The copper(II) ion (Cu2+) origi per ions. Thus, copper is solublein oxidizing the highly explosive copper acetylides CU2C2 nates from the configuration [Ar]3~4?, acids,suchasnitricacid,hotconcentratedsul • Corrosion,inwhichthemetalisattacked and CuC2; therefore, acetylene gas cylinders whichhas aslightlyhigherenergylevel. furic acid, and chromic acid, orin nonoxidiz mustnotbeequippedwithcopperfittings. • Immunity, in which reaction is thepnody Thevalencestatesandtheirradiidetermine ing acids containing an oxidizing agent such ,! namicallyimpossible thespacelatticeofalloysandcompounds: as oxygenorhydrogenperoxide.Forexample, Table8.5:Typicalcoppercontentsofnaturalmaterials. acetic acid attacks copper in the presence of • Passivity, in which there is no cause ofki Mineral Content,ppm Coordination Species number Radius,nm atmosphericoxygentoformverdigris, agreen 'neticphenomena Basalt 85 Diorite 30 CuD 12 0.128 or greenish-bluepigment.Inhydrometallurgi CCuu+2+ 66 00..009762 ciraoln(pilrla)ctsiuclef,atem, iertoanl(IIcIo)mcpholourniddes, asnudchcopas eGdagseesofatnhdebCeohpapvieorr[o3f6s-o3l7id].aAnndleixqaucidtkcnoopwpel r SGCaornapdnpisetteroonrees(poor) 5001001 Thestandardelectrodepotentials(at25°C) per(II)chloridearesuitableoxidizingagents. toward gases is importantfor production and Copperores(rich) 50000 ofcoppercorrespondtotherelative stabilities The other method of dissolving copper is use ofthemetal. Withtheexceptionofhydro Nativecopper 950000 Seawater 0.003 ofthethreespecies: through formation ofcomplex ions. The best gen, the solubility of gases in molten copper Deep-seaclays 200 reagentsforthispurposeareaqueoussolutions follows Henry's law: the solubility is propor Manganesenodules 10000 CIu+~lV of ammonia and ammonium salts or alkali tionaltothepartialpressure. Marineoresludges 10000 Earth'scrust(average) 50 metal cyanides. However copper is essen +0.153V CuD Oxygen dissolves in moltencopperas cop Meteorites(average) 180 cu2+~7V tially not attacked by alkali-metal hydroxide per(I) oxide up to a concentration of 12.65% solutions. CU20 (corresponding to 1.4% 0) (also see 8.4 Occurrence Freshwaterhaspracticallynocorrosiveef These values [31], or thermochemical data Figure 8.22). Copper(I) oxidein solid copper fect on copper, and seawaterhas only a small [32], in comparison with those of other ele forms aseparatesolidphase. effect but wastewater containing organic sul Intheupperpartoftheearth'scrust(16km ments, establish copper as a relatively noble metal. fur-bearingcompoundscan becorrosive. Sulfur dioxide dissolves in molten copper deep), the average copper content is ca. 50 andreacts: ppm. Older estimates were nearly 100 ppm, Behavior in Air. Copper in dry air at room _---- temperature slowly develops a thin protective 1.0 .... -__-- Passivity while recent spectral analysis values are 3D film ofcopper(I) oxide. On heating to a high -- 40ppm. Copperis26thin orderofabundance Corrosion temperatureinthepresenceofoxygen,copper Hydrogen is considerably solublein liquid ofthe elementsin theaccessible sphereofthe forms first copper(I) oxide, then copper(II) > 0.5 copper, and after solidification some remains earth. Table 8.5 shows average copper con oxide,bothofwhichcoverthemetalasaloose ....... dissolved in the solid metal, although copper scale. ro -- does not form a hydride. The solubility fol tentsinnaturalmaterials. In the atmosphere, the surface of copper C'" 0 -- -- - lows Sievert's law, being proportional to the oxidizesin the courseofyears to amixture of 0 .... ......... squareroot ofthepartialpressurebecausethe 8.4.1 CopperMinerals 0- cghreieefnlybaosficthsealbtsa,sitchesuplfaattien,a,wwithhicsohmceonbsaissitcs -'~0" -0.5 Immunity ----- -Z-W.,.(Z-e--=-H-z--- Hso2lumtioolne.cHulyedsrdoigsesonchiaatsehinigtohHdifaftuosmibsiloitnydbies More than 200 minerals contain copper in 0:: carbonate. (In a marine atmosphere, there is (u causeofitsextremelysmallatomicvolume. definable amounts, but only ca. 20 are ofim also some basic chloride.) Such coveringlay -1.0 portanceas copperores(Table8.6)orassemi ersprotectthemetal. o 2 4 6 B 10 12 14 Hydrogen dissolved in oxygen-bearing precious stones (turquoise and malachite). copper reacts with copper(I) oxide at high Behaviorversus DiverseSubstances.While pH_ temperaturestoform steam: Copper is a typical chalcophilic element; many substances scarcely react with copper Figure8.1:Pourbaixdiagramforcopperinhighlydilute therefore, its principal minerals are sulfides, under dry conditions, the rate of attack in aqueoussolutionatnormaltemperature[35]. mostly chalcopyrite, bornite, and chalcocite, creases considerably in the presence ofmois Corrosion [33-34].M.J. N. Pourbaixhas de ture. Copper has a high affinity for free velopedpotentialpHequilibriumdiagramsfor Steamis notsolubleincopper;therefore, it often accompanied by pyrite, galena, or halogens,moltensulfur,orhydrogensulfide. metals in dilute aqueous solutions [35]. Such eitherescapesorforms micropores. sphalerite. 498 HandbookofExtractiveMetallurgy Copper 499 Table8.6:Themostimportantcopperminerals. intheWestern.world.Therearemanyexam • Deep-sea concretions lie in abundance on Mineral Formula Copper Crystalsystem Density,gfcm3 ples of different types ofhydrothermal de thebottom ofthe oceans, especiallythe Pa Nativecopper Cu ::;99.92 cubic 8.9 posits. Examples: Butte, Montana (gangue cific Ocean. These so-called manganese Chalcocite CU2S 79.9 orthorhombic 5.5-5.8 deposit); Tsumeb. Namibia (metasomatic nodules couldalso bea source ofcopperin Digenite Cu9S5 78.0 cubic 5.6 deposit); Bingham Canyon, Utah; Chu thefuture. Covellite CuS 66.5 hexagonal 4.7 quicamata, Chile; Toquepala, Peru; Bouga Chalcopyrite CuFeS2 34.6 tetragonal 41--4.3 Bornite CU5FeS4fCu3FeS3 55.5-69.7 tetragonal 4.9-5.3 inville, Solomon Islands (impregnation 8.4.3 CopperOreDeposits Tennantite CUt2As4S13 42-52 cubic 4.4--4.8 deposits). Impregnation deposits are also Tetraedrite CU12Sb4S13 30--45 cubic 4.6-5.1 calleddisseminatedcopperoresorporphyry Enargite CU3AsS4 48.4 orthorhombic 4.4--4.5 Geologically, the main regions of copper Bournonite CuPbSbS3 13.0 orthorhombic 5.7-5.9 copper ores (or simply porphyrIes) because ore deposits arefound in two formations: the Cuprite CU20 88.8 cubic 615 - oftheirfineparticlesize. Precambrian shields and the Tertiary fold Tenorite CuO 79.9 monoclinic 6.4 Malachite CuC03·CU(OH)2 57.5 monoclinic 4.0 • pxhalative sedimentary ore deposits origi mountains and archipelagos. There are major Azurite 2CuC03·Cu(OHh 55.3 monoclinic 3.8 nate from submarine volcanic exhalations producingcountriesoneverycontinent[38]. Chrysocolla CuSi03·nH20 30--36 (amorphous) 1.9-2.3 and thermalspringsthatenterinto seawater, Dioptase CU6[Si601B]·6H20 40.3 rhombohedral 3.3 • North America: United States (Arizona, Brochantite CUS04·3Cu(OH)2 56.2 monoclinic 4.0 and constitute a transitional type to sedi Utah, New Mexico, Montana, Nevada, and Antlerite CUS04·2Cu(OHh 53.8 orthorhombic 3.9 mentary deposits. These ores are third in Michigan), Canada (Ontario, Quebec, Brit Chalcanthite CuS04·5H20 25.5 triclinic 2.2-2.3 economic importancein theWestern world. Atacamite CuCI2·3Cu(OH)2 59.5 orthorhombic 3.75 The actual formation of such sulfidic pre ish Columbia, and Manitoba), and Mexico (Sonora) Secondary minerals are formed in sulfide 8.4.2 OriginofCopperOres cipitations can be observed, for example, ore bodies near the earth's surface in two themarineoreslimesintheRedSea.Exam • SouthAmerica:Chile,Peru,andBrazil Ore deposits are classified according to stages.Intheoxidationzone,oxygen-contain ples: Mount Isa, Queensland; Rio Tinto, theirmodeofformation, buttheoriginofcop • Africa: Zaire, Zambia, Zimbabwe, South ing waterforms copper oxides, subsalts (sub Spain;Kammelsberg(Harz),Germany. per ores is geologically difficult to unravel, Africa,andNamibia carbonates and subsulfates), and silicates. In and some ofthe proposed origins are contro Sedimentary Ore Formation. The origin of • Australia and Oceania: Queensland, Papua the deeper cementation zpne, copper-bearing versial. The classification distinguishes two sedimentaryoreoccursintheexogenouscycle NewGuinea solutionsfrom thesesaltsaretransformedinto maingroups, themagmaticseries andthesed of rocks and may he subdivided into the fol secondary copper sulfides (chalcocite and imentaryseries. lowinggroups: • Asia: Russia (Siberia, Kazakhstan, and covellite)andevennativecopperofoftenhigh Uzbekistan), Japan, Philippines, Indonesia, Magmatic Ore Formation. This involves • Arid sediment in sandstones and conglom purity, e.g., in the Michigan copper district magma crystallization and comprises the fol eratesoccurwidelyinRussiaas widespread India,Iran, andTurkey (KeweenawPeninsula). lowinggroups: continental zones of weathering with un • Europe: Poland(Silesia),Yugoslavia, Spain Othermetallicelementsfrequentlyfoundin • Liquid magmatic ore deposits originate by even mineralization. Examples: Dsheskas (Huelva),Norway,Sweden,andFinland copperores areiron, lead, zinc, antimony, and segregation of the molten mass so that the gan,Kazakhstan;Exotica,Chile. Antarcticamaybeanimportantcopperores arsenic; less common are selenium, tellurium, heavier sulfides (corresponding to matte) • Partly metamorphized sedimentary ores in intheforeseeablefuture. bismuth, silver, and gold. Substantial enrich separatefromthesilicates(correspondingto shales, malls, and dolomites form large ments sometimes occur in complex ores. For slag) and form intrusive ore bodies. Exam strata-bound ore deposits, especially in the Table8.7:Copperorereservesin1983ofthemostimpor tantproducingcountriesoftheWesternworld[41--42]. example, oresfrom Sudbury, Ontario, in Can ples: Sudbury, Ontario; Norilsk, westernSi African copper belt, and represent the sec ada contain nickel and copper in nearly the beria. ond most important source ofcopper to the Country Orexre1s0e6rvtes, wPeorrcldenretasgeervoefs • Pegmatitic-pneumatolytic ore deposits de Western world, as well as supplying nearly same concentrations, as well as considerable velop during the cooling of magma to ca. 75% ofits cobalt. Examples: Zaire (oxida UnitedStates 99.6 21.1 amounts ofplatinum metals. The copper ores Chile 96.5 20.5 374°C, the critical temperature of water. tion zone, oxidizedores:::;6% Cu);Zambia from Zaire and Zambia are useful sources of Peru 30.6 6.5 Examples:Bisbee,Arizona; Cananea,Mex (cementation zone, secondary sulfide ores, Zambia 30.3 6.4 cobalt.ManyporphyrycopperoresinAmerica ico. :::;4%Cu). zaire 29.6 6.3 contain significant amounts of molybdenum Canada 27.4 5.8 • Hydrothermal ore deposits resultbyfurther • Marine precipitates have formed sedimen Mexico 23.1 4.9 and are the most important single source of cooling ofthe hot, dilute metal-bearing so tary ore deposits similarto the presentphe Australia 16.1 3.4 rahnednoiuthme.rrTahreeeelexmtreancttisocnanobfepdreecciiosiuvsefmoerttahles lloutwionthsefrcormiticcaal.t3e5m0p°eCratduorwenowfawrdat,eir..e.S,ubceh nbaocmteernioaninotfhesudlfeipdtehsporefctihpeitaBtlioacnkbSyeas.uElfxu r PPPhaapniluaipmapNaineewsGuinea 111201...789 222...753 profitabilityofcoppermines,smelters,andre deposits contain copper primarily as chal amples: Mansfeld (copper schist), Ger Brazil 10.0 2.1 fineries. copyriteand satisfy ca. 50%ofthedemand many;Silesia(coppermarl),Poland. Total 398.6 84.5 500 HandbookofExtractiveMetallurgy Copper 501 8.4.4 CopperResources tensive mechanization. The high cost of ciallyequippedshipshavecollectedandlifted • Beneficiationbyfrothflotation togetacon miningandoforebeneficiationcontributesup these nodules from depths of 3000-5000 m; centrate The copper contents ofthe worldwide pri totwo-thirdsofthefmalpriceofcopper. specific metallurgical and chemical methods • Optional partialroasting to obtain oxidized mary copper reserves are listed in Table 8.7. There are several methods of mining cop for processing the nodules have been devel materialorcalcines Reserves are the identified (measured, indi perores: opedinpilotplants.Becauseofthe extremely cated, and inferred) resources and do not in • Two-stagepyrometallurgicaltreatment • Open-pit(surface)mining high expenses, large-scale operations of this clude undiscovered (hypothetical and typehavenotyetbeen undertaken.Marineore a) smeltingconcentratestomatte speculative) resources. In the course oftime, • Underground(deep) mining slimesfrom theRedSea(2200-mdepth) aver b) convertingmattebyoxidationto crude theavailablereservesincreaseinconsequence • Insituleaching(solutionmining) age ca. 4% Zn, 1%Cu, and a little silver. Al (converterorblister)copper ofboth technologicalprogress in theprocess • Oceanmining though methods for processing these'slimes ingoforeswithlowcoppercontentorundesir Atpresent,thegreatestpartofprimarycop have been investigated. this resource is not • Refming the crude copper, usually in two steps able impurities and the discovery of new ore per comes from open-pit mines, mostly from now economicallyimportant. deposits [39--40]. In 1982 the world reserves porphyry ores. The first open-pit mine was a) pyrometallurgicallytofrre-refmedcop were estimated at 505 x 106 t ofcopper. The startedatBinghamCanyon,Utah, earlyinthis 8.5 Production per total land-based resources were estimated at century; other big mines are found in Chu b) electrolytically to high-purity electro 1.6X 109tofcop~er.Inadditionthereisanes quicamata, Chile and Toquepala, Peru. Profit lyticcopper Overthe years copper production methods timated700X 10 tofcopperindeep-seanod able open-pit production requires large ore have been subjected to a continual selection About 15% of the primary copper origi ules. bodies near the surface with a minimum cop process because of the need [45] for (1) in nates from low-grade oxidized (oxide) or Ifoneassumes thattotalproductionwillre percontentof0.5%(in some cases, as low as creased productivity through rationalization, mixed (oxidized and sulfidic) ores. Such ma main stable, the identified resources would 0.3%) in sulfidicform for subsequentbenefi (2) lower energy consumption, (3) increased terials-aregenerallytreatedbyhydrometallur lastuntil ca. 2050,which is thestatic outlook. ciatingbyfrothflotation. environmental protection, (4) increased reli gicalmethods. In contrast, the dynamic approach which as Undergroundmininghasbeenpracticedfor abilityofoperation,and(5)improvedsafetyin The very few high-grade or rich copper sumesthatproductionwillincreaseattherate millennia. However, in the last few decades operation. During this developmenta number ores still available can be processed by tradi it has in recent years, would reduce the dura the competition ofopen-pit mining has made oftendencieshavebecomeapparent: tionalsmeltinginashaftfurnace.Thisprocess tion ofknown reserves by nearly half. Ifone such older underground methods as overhand is also used for recovering copper from sec • Decreaseinthenumberofprocesssteps , considers all copper resources, these times and underhand stoping uneconomical. Newer ondary materials such as intermediate prod would be at least doubled. However, all of proceduressuchas openstopingorblockcav • Preference for continuous processes over uctsscrapandwastes. these forecasts are quite unreliable. In addi ingcan beusedifgoodoresoccurindeep de batchprocesses Figure 8.2 illustrates the most important tion, the forecasts do not take into consider posits. The copper concentration should • Autogenousoperation operations in copper extraction from various ationsecondarycopper(recyclingscrap). exceed 1%, and some content ofotherprofit • Useofoxygenoroxygen-enrichedair copperores. ablemetalsisdesirable. • Tendencytowardelectrometallurgicalmeth 8.4.5 Mining Insituleachingisahydrometallurgicalpro ods 8.5.1 Beneficiation cess in whichcopperis extractedbychemical • Increased energy concentration per unit of Exploration, whichisthesearchfor orede dissolution in sulfuric acid. This method is Mostsulfidecopperores mustbebenefici volumeandtime posits andtheirsubsequentdetailedinvestiga suitable for low-grade copper ore bodies for ated to increasethe metal content. The essen tion, is required to ascertain the commercial which customarymining operations would be .. Electronic automation, measurement, and tial operation is froth flotation, which is feasibility ofa potential mine. Manygeologi uneconomical as well as for the leaching of control usuallycarriedoutintwosuccessivesteps:the cal, geochemical, and geobotanical methods remnant ores from abandoned mines. Insome • Recoveryofsulfurforsaleordisposal firstis collective orbulkflotation for concen are available, but all are complicated and ex cases, the ore body must be broken before • Recoveryofvaluablebyproducts trating all the metal-containing minerals, and pensive. Often legal and political factors are leaching by blasting with explosives-to in The selection of a particular production the second, ifnecessary, is selective flotation moredecisive than technologicalaspects. The creasethesurfaceareaforchemicalreaction. method depends essentially on the type of toseparatethevariousminerals [47]. average coppercontentofores is an essential A recent development is ocean mining, available raw materials, which is usually ore Figure 8.3 shows the reduction in total factor.In 1900,thiscontentworldwidewasca. which involves obtaining metalliferous raw or concentrate and on the conditions at the mass with simultaneous enrichmentofcopper 5% Cu. Today it is ca. 1%; nevertheless, this materials from the deep oceanic zones. Two plantlocation. contentinthestepsfrom oretometal.Modem representsaca.200-foldenrichmentoftheav groups ofsubstances are ofinterest: deep-sea About 80% of the primary copper in the dressingplantsarealwaysbuiltnearthemines eragein the earth'scrust. High-gradedeposits nodules [43] and marine ore slimes [44]. The world comes from low-grade or poor sulfide toreducethetransportationcostsand are con (>6%Cu)arelargelyexhausted. nodules(manganesenodules)contain,inaddi ores, which are usually treated hy pyrometal structed in a relatively uniform manner. The Foreconomicreasons,modemcoppermin tion to iron oxides, ca. 25% Mn, 1% Ni, lurgical methods, generally in the following frrst operation is the comminution of lumpy ingmusthavehighcapacity,which means ex- 0.35% Co, and 0.5% (max. 1.4%) Cu. Spe- sequence: orestoapulpinthefollowingstages: