UNI PROCESSES OF EXTRACTIVE METALLURGYa CONTENTS Preface Chapter 1 Introduction 11, Sue of Metals 1 Copper 2 esd 2 Ta 2 ‘Titeniutn and Manganese. 4 42, Miner! Engoseting 4 Ea, Extractive Metallurgy 4 4. Charmin! Metalsgy in the Extrtion of Maal 5 Chapter 2 Pyromstallurgy 1. Roasting—Agolomeration—Caleination 24, Roasting of Slfde Ones 1 Thecodynaiies of Boasting Reasons. 7 Volatilation During Rossing 2 22 Industral Rosatng Processes 2 Mechanical of Hearts Roaring 2 Flash Ronsting 8 Fluid Bed Tossing 18 Siter-Roset, 6 28 Sintenna 6 ul Roqsirment is ngatering elatoathipe far Desig of Sintering Opoations 0 Const 0 D4 Palatinng 0 25. Calenation 2 Thermodynamics of Casination 2 Kinetic beckaine of Caleinaion 23 Chapter 3 Pyromealluray II. Ozidation—Redustion Reactions 5:1, Thoradynatmie Stability of Mingral Compounds Trermodsnaile Stblity of Oxides Crrbon-Owgen Pqulibria—Toe Bouduard Reaction ‘Thermadynamie Sioliy of SulBdes Reducbly of Chlorides Stabity of Carder and NitridesChapter 4 Chapter 5 Contents 32. Osidation—Radueton Reactions Involving Liquid Metalic Sox “Thermodynamics of Metallic Soaions Nonideal Soltions Dilute Solution Bebavion Conversion from One Standard State to Another Solute Interactions in Dilte Solutions. 8.3, Iaduseal Appeation of Reduction Rewtions ‘Krall Proce, Produtio of Tange Padgeon Procest Casbotheraie Reduction of Magnesia and Alumina Extraction of Zine adm Production. Mercury Prluction ‘The Mond (Carbonyl) Nickel Proce. Direct Reduction of lon Ove Several Cominerial Prose for Diret Reduction of Ton Oree Pyromstallurgy IIT, Smelting and Converting 1-1. Revorberatory Seating ‘Tin Sree Copper Sting 42 lat Furnace Smeting “The Lend Biaet Furnace The [ron Bast Furnace Chemisty of the Iron Blast Burmace, lant Furoaor Stoichiometry ney Balance Trmprovemente a lad Furoace Operation 43, Avtogenus Setting 44 Copper Converting 45) Stelmaking Benet Converter Process (Open Hearth Process. Oxygen Stealing (Oxygen Convertet Gas Recovery Proceses aldo and Rotor Procemes, 7 <~Spray Stemabing Blectne Furnace Stesinaking Pyrometalturgy IV. Refining Processes Gl. Liquid Phase Refining Dendation Equi ‘Aluminum Deosidation of Stee Sunnary of Deowtdtion Data, Precipitation Stoichiomsty Desulfurzation of Molten Pig roa asks Prose “Mints of Nuchation of « Separating Paso GGrowh and Flotation of « Seperating Phase 7 ” - 2 2 Po st a a1 05 108 108 19 13 ne Contents Chapter 6 Chapter 7 Liquid Phase Separation ‘Processing Operation Lead Silver Sytem. Lead-Copper Stem. Zine Recovery by Las Phave Separation. Enginering Design Process Yel Purity of Product. ‘Thermal Requirements Proce Kinetics Refning by Ovidation Scoondary Metal Refisiog 52, Dailatson Processes (Clnus-Clpeyron Equation. Rlaive Valaiy Eaullosium Distilaon ‘Meleclar igilstion ‘Vaeuum Desincing of Deilverized Lead Bullion DOteervstone on Liga Tron Alloys. 53. Degassing Operations. Fundamentals of Gar Meta! Restons Diseomie Gass Compound Gases Inert Flash Degas ‘in Fibs Proce Boundary Lager Mode CCaleulation of Residence Tie Other Degasing Processes “Temperature Drop of the Melt Ding Dogesing Hydromealturgy 6:1, Hydrometallurical Proeses, Leaching. eaohing Tecalques Recovery of Metal from Suton “Thermodyaaiies of Reduction of Metals (om Solution lected Potentials, ‘The Hydrogen Electrode Meta-Metl Ton Electrode Potential “Hydrogen Redvetionof Metal Tons Kinetesk Gass Reductin in Aqueous Soutons Other Resovery Methods. 62, Indust Hydrometrgical Operations. Hydrometallurgy of Copper Gold and iver Hiydromesalisgs Uranium Hydrometallrey Zine Hydrometallegy. Hydometallugy of Nese and Cobal HYydeometallurgy of Aluminm-Bayer Pros. Eletrometallurgy TA. Prnspln af Electrol Halsell Reaction, 116 ie rr ir a 10 10 a 2 rf Mi Mi ra 18 48 1s 152 155 13 187 ie 9 io iso 81 is. 185 1s 101 01 01 1 196 195, 15 m1 2Chapter 8 Chapter 9 Faraday's Laws, Reverb Call Potent Call Votage. ‘nove Resistance, Reverble Cel Potoni Polasastion Over-Vetage. 72. Hlctotae of Posed Salis ‘slumiaum Hal Qeroal) Proce Cll Petenta Mageasus, Sodlusn 73, Flecsoliie Refing Copper Refning ‘node Preparation Refi Speers : Tank Hone Practice ‘Trealment of Tnslubes Refining of Copper Cathodes Nickel aed Lead Roig Enetzo-Winntag Metals om Leaching Saitons Melting, Pouring, and Solidification BA. Making Pacis, ‘Thermal Requirements for Melting Matting Units Sensible Heat o te Metal Seosible Heat of she Matting Unt Host Losses Mase and Enon Balance on Sling Vat. Pouring Operations, ate of Powring “Temperate Drop. 83. Chsting and Solsfeation Rate of Soiintiog Ingo Structure ‘ict of te of Heat Removal on ingot Strain Taflucooe of Metal Composition, Tesuenee of Shckage Etec of Disaved Gass Deters in Tagous 84. Continuous Casting 85. Other Catiag Procdares, Computer Applications in Estractoe Metallurgy 841, General Nature of Digtal snd Analog Computers ‘The Digial Compuset ‘The Aeaiog Computer 92, Applistions of Electonie Computers Comparisos of Analog and Digital Machines Extractive Metallurgy aud Systm Enginerog 229 2 20 26 238 an 2 28 Bn 2 246 28 oar 250 2s 258 250 254 261 28s 288 268 Contents Appendix A Appendix B Index 9.3, Matera HandingA Queueing Theory Approch, Quetcig Theory Sale Station Queue Problem Exam in of Single Saitn Queuing Prblem Multsteion Queusiag Problem Exar feof Maltsation Mode! (Other Approashes to Queusing Problems 94. Linear Proganiaiog Applications of Lines Prograsiting 25 Prom Simulation Table Ad, Summary of FreEnergy Bquations for Sulfation Resetons ‘Table AL Standard Free Enurgice of Formstion af Compounds at ‘Stelaaking Temperate ‘Table ATE. Activity Concent ¢ Tafite Dilution fa Ligud Metal Table A-IV. Standard Pree Energy of Solution of Vasius Elements ia Liquid Tron ‘Table ALV. Intention Coeficiente Vor Elements Diswived in Ligud Tron 2 190°C. ‘ahie AVE Nonieeous Interaction Baramtere. ‘Table ALVIL. Vapor Prenuros of Liguld Metals ‘Table AVIIL Standard Elstode Potentials at 25° fr Ordaton Rese ‘Table ATX. Heat Content of Seven Metals ‘Table AX The Eror Function Example Problems and Computer-Facitiated Solutions Exarple Problem No.1: Thertmoshemieal Date Calsulatlon-Enthalpy Tectia Example Problem No. Caleulaion of bt Flaie Tomperatar atthe Fayre fs Coke-Fasl Shalt Fucnace. Example Proslam No.3: Cooling of Pi Ion in a Trandfr Ladi Example Protas: No.4 Precetng the Scrap Regulmeat for the Oxy” ten Stoalmaking Procoss Btample Probless No.5" Digital Compurer Avalyas of Heat Faw and ‘Tempecature Distibutlon Around & Copper Caateriae Tayere. Beample Prctieat No. Heat Lote Through a Furnace Rect snple Problam No. 7: Digital Computer Simulation af @ Boitom- Pouring Ladle Example Probie No.8 Unsteady Stat Heat Fow—Coolagof «Sab Example Protlam No. 9: Ligesr ‘Reghesnlon Analy “BOF Stee “Cherie. [Example Probl No 10: Tinea Programing -Optimantion of Cup ‘Charge 298 Ey on sis 8 as a 8 Es su aePreface For over a decade the ned has existed for a college textbook on extractive metal- lurgy which refiets developments in the technology and science of this engineering area, In particular, the use of chemical thermodynamics to deseribe the behavior ‘of metallurgical processes has developed extensively and is now an integral past of the engincering approach to process analysis. During this same time interval, the use of computers has become increasingly important in engineering practice. This text places strong emphasis on the use of both engineering tools as applied to extractive metallurgy Moat educators in the field of extractive metallurgy have recognized thet a unit process treatment of the subject has much more to offer than deseriptive presenta fion of current practice on @ metal-by-metal basis. This text is based on the unit process concept. and emphasis is placed on basic principles rather than detsiled Dractige, Nevertheless, some descriptive material has been included to provide a background and engineering context for the student. The instructor can utilize Ieetures and assigned reading to extend the description of industrial practice while ‘emphasizing fundamental principles as presented in the text. An attempt has beer made to extend the unit process ecneept to consideration of the design of entire ex- tractive processing systems. ‘The future of metallurgical process engineering undoubtedly williavolve, in ad- dition t0 the advances in metallurgical science, techniques which are adapted from chemical engineering, instrumentation, eamputing science, economies, operations research, and other alliod fields. The metallurgical engineer should be acquainted With these areas, at least to the point of being able to evaluate possible contribu- tions to metallurgical processing operations by specialists from these related fields cally, the trained metallurgist should be prepared to assume a position of leader- ship in the engineering team which handles the multi-faceted problems af metal Iurgical process design and operation. This book reflerts an effort to expand the teaching emphasis in extractive metallurgy, and includes an introduction to some of the fields which are portant in metallurgical proceasing systems. In addition to an azslytical approach to the engineering of metallurgical unit processes, the text in- cludes introductory material on the use of computers in process engineering, opera- tions research procedures which treat system behavior in terms of queueing theory or linear programming models, and mathematical simulation of processing systems. ‘The objective of providing.a textbook on extractive metallurgy for the junior, senior or beginning graduate student placed constraints on the text. ‘These com straints prevented extensive development of each subject area in the broad field encompassed by extractive metallurgy. On the other hand, adetailed development of several subjects is included to emphasize the rigor and thoroughness characteristic of sound engineeringxiv Preface “The testis developed on the basis of three altemative approaches to metal ex- traction and refining: pyrometallurgy,hydrometallurey, and electrometallurgy. These production alternatives have their roots in physical chemistry but draw upon many Twlated fields, Furthermore, these three stems of extractive metallargy are not inde- pendent, but often are combined in many extraction and refining systems. Pyro~ metallurgiea\ unit processes are developed in considerable detail in the first several chapters, followed by hydrometallurgical, ena elecrometallurgieal processes. A chapter on melting, pouring and solidification then follows which involves topies on pytometallurgy but is focused toward the semi-finished product. The text concludes ‘sith a chapter covering the principles and techniques for computer-oriented analysis of extraction and refining systema. ‘Traditionally the teaching of metallurgical engineering hes been problem oriented. Some engineering problems have specific solutions. Other problems bave a range of solutions, some of which are more optimal than others. Both types are ‘encountered in engineering practice, and therefore both have been included in the text. In all eases an effort is made to emphasize the underlying basic principles. “Example problems are a useful supplement in the study of the text materia. ‘The text contains a number of such problems as worked examples. Problems and discussion questions are provided with each chapter. The text. and problem sets fare self-contained. However, the discussion questions, while based on material intro- duced in the text, uggest avenues for further study ‘An appendix of problems with documented computer solution is included to il- lustrate the application of this modera technological tool. The problems and ap- proaches to solving them illustrate a variety of numerical methods which ean be implemented on the digital computer. Phe problems have been selected on the basis of their pertinence to engincering practice and hopefully they will have applications beyond the college classroom, Twish to thank all those who have helped if the preparation of this book. The evelopment of thie text bas involved several years of teaching & senior course at ‘The University of Michigan entitled Metallurgiea) Proceas Design. The students in those classes as well as many interested graduate students contributed immensely to the text material as it developed. Many colleagues and peers, both in industry ‘and in academé, have generously contributed suggestions, comments and encourage- ‘ment, Special recognition goes to Ralph D. Higgins who reviewed the early manu- seripts, to Elaine Galoit who typed the final manuscript, and to Robert E. Marrone ‘tho assisted in preparing the computer appendix, to name only a few of the many tho contributed. I am grateful to my students for their inspiration and to my family for their help, encouragement, and understanding. Robert D, Peblke ‘Ann Arbor, Michigan CHAPTER 1 Introduction Within ¢he broad field of metal soiencos and technology, the initial peogesing stops are extraction and refining. Theso extractive and purification processes, the subject ofthis text, are built upon the principles of chemicel metallurgy. Chemical sotallurgy (a8 contrasted sith physical metallurgy, the study af the solid state and the structure and properties of metal materials) utilizes physical chemistry, draws ‘upon inorganic chemistry and electrochemistry, and depends upon some areas of organic chemistey to describe metallurgical systems, The unit processes of extractive metallurgy ace presented in this text with emphasis on the underlying chemical metallurgical principle, 1-1 Source of Metals ‘The original source ofall metals is the earth's crust, which contains metallic deposits ‘usually in the form of their oxides of sulfides called ores, from which metals can be extracted. In some instances, noble metals, sueh as gold, silver, and sometimes opper, are found in native oF free elemental form, Ores are seldom composed of one ‘metallic compound but usually are made up of several, including the mineral of the desired metal as well as other impurity compounds refered to as gangue. The impor- tant minerals of the most common metals are listed by name and chemical formula, in Table 11 Ores are found in a wide variety of locations snd at various depths in the crust of the earth, Ores are mined by underground methods or by surface mining tech- niques, such as open pit of strip mining. Magnesium is obtained primarily from sea water ‘The virtually inexhaustible supply of many common metalic elements is Teflected by the large amounts of iron, aluminum, silicon, esleium, sodium, and ‘potassium in the earth's crust. In the case of magnesium, a vast supply exists since each eubie mile of sea water contains several million tons of magnesium, A very important metallic element is iron, which accounts for the largest past of the metal industry. ‘The primary source of iron is from the minerals magnetite (Fe,0,), hematite (Fe,Q:), and limenite (Fe(Os plus some combined water); the concentration of iron in high-grade, direct smelting ores may range as high as 60%, bat ores containing only 25% iron have been smelted. ‘The priecipal souree of high grade ore within the United States is the Lake Superior district in Upper Michigan ‘and Minnesota. Other important deposits still exist in the Lorraine Basin of France, the English Midlands, the Doneta Basin and the Ural Mountains of Russia, and in northern Sweden. Important deposits which are being mined include those in2 Unit Processes of Eatractive Metallurgy Tatraduet tution 3 northern Quebec, Labrador, Brasil, and Venesuela, Until recently, the readily ‘rane vt ‘available, ton-bearing minerals were of sufiiently high grade that little attention 0 was paid to methods for concentrating them, but depletion of high-grade deposits ‘has led to development of techniques for concentrating low grade ores, one of which Minette of Common Meta taconite plentiful lowegrade iron ore containing approximately 907 ion, (a wet Miaeat Forman sta the fon onde is fnelydisperedthroughowt @sikea matrix. The upgrading a _ Stason soeomplished by grinding and condentration, followed by aggion~ nn aman tration into pees for charging to the iron blast urntee ‘eu Copper ix found i nature inform ranging from the pure metal to sulfide, tent a cide, sed embonate. The pure meal is foun in appesable amouits only inthe . Serie Upper Peninsula of Mickign, bt thse “lake copper" deposits are nearly depleted Conger Nae Cont El do aot now represent an important soure of eoppet. Coppers mast commonly Sia iDund sacle, either chalet, chaleapyit, or covelte The action of uraee Se ie winer on slide minerals of eoppet leads to oxdatio, andthe upper portions of . Sunne Copper ore dapat are esualy hig in copper ones, Copper ores are utaly Iw in uninas Disae NS en0 copper onten, containing let than 8% eoppet, but ores containing as litle ax otis Mavato Peng copper can usualy be proceed at prot. Shipping costs fr thes l= vat Boles sae as008 Frade oe deta that concentration facie Ye located a the mine. Tee principal Serle foo, Scorssof copper are the Cordillera afte western Unite Sates and South Amerie, fiote rs! the Central Ngan Platen in northern Rhodesia and Katanga province of the tine Sota 28 ne Mend) Belgian Congo, and the Canatian Shield. The largest and richest coppermine in Ten thetworld fs 8¢ Chuguicamata, Chile, nd the second largest mie i in Binghatt asp Fook Geto. M Canyon, Uiah Dole ECO, cacOs "Thumm i one of the most abundant. metalic elements and represents re Cann Ro. apprenimatly 8% of the eats erat, occuring as the oxide Although several Scie (Cos-nes-08) tmawcals conta appreciable amounts of minum, the only ore Uilzed com- Nie Mier NS oy ve ete ffbbste and diaspote, These oes are sausliy found ia copical ot sub ropieal enlaite gray S Smats, the mote important sources of ommerdal bauxite being in Sunnam, Mangsnete Fytate Sino. {Bridah Guian, Jamie, and Indonesia Other deporte are being minedinsouthera botocste Me, United States and at several oetios in southern Europe chroium Bhatia seso. San nd karl ar ws wats a Gene Gees Ra often snverted upper portions of leas deposits co the silat aaglesite or the fe ro, Gdrbonace eerste, The ores of lead usualy contin, im addition to zine biende resin Bidiote By {ere below), recoverable amounts of copper, iver, gold, antimony, and bismuth \ on 2s. {Pre large producers of lead include the United States, Australia, Rusia, Canad, jsut Pavone VS suo and Mesico. Appreciable quantities of lend ae also produced in South’ Americ, eadints Fm VOONO the principal sources bing Per Baie, aad Arguing Mobienm Meyda Mss The tost important sine mineral eth slide sphalerit, often refered o as Moye sto. sine blend, The taneralssphaleie (ZnS) and glans (PbS) Realy alvays occur ‘Tunes Wetiamite FeO, together anda sting af the principal sin-prodiing reins Would be esetilly sive Stee” CaO, {ie same autho fr lead. Phe ony exception where aibe deposits do not also Xaves has ‘Sutse appreciale amounts of lead i at Franklin Furnace, Nev Jersey, where ome MS {fe depose area mintoe of incite and the itn and manganese-bearig mineral oa Sheet vee ‘ante, franklinite Tinis a relatively raze metal, agcousting for les than 0.001 wt % of the earth's Sylvanite (susoree4 Unit Processes of Hatractive Metalursy ‘TABLE 1-1 (Contiued) Metal Mineral Formula Beerliam Bey 3B20-A10,-680, Merry Cinnabar ys Veena Pehblende Comes oxide Csdnivn Greenteie cis ‘auimony Scinie SHS Cabal Cobalite cons ‘rust, The most important mineral of tn isthe oxide cassiterte, Asa heavy mineral, tin oxide is often concentrated into a placer deposit by the action of Water breaking down igneous rock both by physical and chemical means and thus concentrating the heavier minerals. These placer deposits are located principally in Malaya and Indonesia, where the tin is recovered by hydraulic mining techaigues, often em- ploving dredges with sal-contained equipment for concentrating the ore. Bolivia has substantial tin deposits. The tis is mined there by open cut methods where it ‘occurs in vein deposits as the mineral stannite. Titanium and manganese are relatively common metals, aecousting for 0.1- 1.09% of the earth’s crust. Titanium occurs as ilmenite or rutile, and these deposits are located in the United States, Canada, India, Australia, and Brazil. Manganese occurs primarily as the oxide pyrolusite; the primary producer is the USSR, secounting for about one-half of the world output. Other important producers of ‘manganese include India, Ghana, South Afriea, Brazil, and Morocco, Other metals such aé gold, silver, cadmium, bismuth, arsenic, ete, are the ‘by-products of eopper and lead production. Most other metals are found in relax tively small, low-grade deposits in the form of minerals listed in Table 1-1, 1-2 Mineral Engineering Mineral engineering, the fist major step ia the extraction of metals, involves the separation and concentration of ores. These concentration techniques, which are primarily physieal or mechaniea! separations, ate referred to as mineral dresing Tis outside the seope of this text to diseusstheze concentration techniques in any detail, However, it should be noted that the economies with which the extractive rmetallurgst must work in optimizing his proceses for smelting and refining of ‘metals depend very much on the raw material With which he is working, Those raw materisis ate the product of the aredrestng step. 1-3 Extractive Metallurgy Following ore dressing, the removal of any rerasining gangue, decomposition of the ‘metallic mineral to produce s metal, and subsequent refining of the metal are the functions of extractive metallurgy, Extractive metallurgy ean be divided into three Introduction 5 ‘TABLE 12 9 World and United States Production of Principal Metalee World proiin- U.S.A. produc. Percentage est tion thousiods tion (thousands of word of shor tons) of sort tons) Tron Pig iron and feroaioys 7,558 a Stel ogota and casting 2 Atuminue a8 Copper a Zine 1% Tea 7 Magness S «From Minerale Yearbook, Vo. Land TE, Mutt, Minas and Ful, US, Dept ofthe Interior, Bares of Minas; US. Goverement Printing Of, 191 principal areas or types of processes: 1. Pyrometallurgy, which employs high temperatures to carry out smelting and refining reactions and melting operations. 2, Hydrometallurgy, which employs liquid solvents, usually aqueous, to separate the desired metal 8, Eleetrometsllurgy, which employs leetrical energy, principally for carrying out electrolysis to nxtract and refine metals ‘The type of process or sequence of processes used depends to a great extent upon the starting material, ie, the mineral concentrate, and the desired product. Selection of the particular process also depends upon the local economics, including the facilities available, power and fuel costs, and other factors such as the aceassi- bility of water, shipping costs, avsilability ofthe market, ete, These considerations, slong with the demand for various produets end the availability and costs of ores, have determined the makeup of today’s world metallurgical industry. A general Picture of that industry is provided by Table 1-2, which lists the world and United, ‘States production of prineipal metals for the year 1969. 1-4 Chemical Metallurgy in the Extraction of Metals Following the mining and concentration of minerals, their extractions arcomplished by application of chemical metallurgy in one of the three areas of extractive metal lurgy: pyrometallurgy, hydrometallurgy, oF eleetrometallurgy. In the following chapters these topies are treated in detail. Pyrometsllurgy is discussed in terms of the roasting of ores to convert sulfides to the more easily processed oxides. The physical chemistry of roasting and ealeining reactions is presented and agglomerating techniques are discussed. The prineiples of oxidation and reduction resetions are6 Unit Processes of Katractve Metallurgy presented in terms of application to smelting of minerals by reduetion to the metallic state or to & fused sulfide (matte), and gonversion to a semi-refined metal. Subse quent pyrometallurgical refining procesee, distillation, liquid phase refining and degassing operations are quantitatively diseussed in terms of thermodynamiv and Kinetic limitations. Hydrometallurgical and eleetrometallurgical processes ae r0- viewod. Then the pyrometallurgice! processes of melting, pouring, casting, and solidi~ fication are described. Finally, computer applications in the field of extractive metallurgy are developed, along with the presentation of example programs, Bibliography Dennis, W. H., Bsiractiny Manilurgy, Philosophical Lissey, New York, 196, Gaudin, A. RC Flotation 2a ed, MoGraw Hl, New York, 195 Giices, J.D Eetation Maltrgy, Pergamon Prov, London, 1967, Hayward, ©. sin Olin Atafergia! Prac, D. VanNcstrand Co., New York, 1952 Newton, tue Mealergy, Joba Wiley, New York, 1959 Pryor, B4, Mineral Procasing, Mining Pubintions, Ue, London, 190, ‘Tagaare, AE. Blea of Ore Drssing, John Wiley, New York, 105 faggar, A. F.,Handbook of Mineral Dreming, John Wiley, New Yor, 106, Discussion Questions 1, Develop a correlation between the current market price of the more common. metals and their level of production or use. What are the major factors in ‘estabifhing these relationships? 2. What are the current price levels for serap as contrasted with ingot or primary material for common engineering metals? Discuss the role of secondary metal in each metal market. 3. At what eonoentrations of mineral are the principal mining operations being ‘worked to recover the major metals? 4. In extracting and reining aluminum, copper, zine, lead, mereury, niekel, Cungsten and magnesium, a key unit process is used. Considering the chemical snd physical properties of the metal and its mast common mineral state which process is applicable to each metal and why the particular provess is used CHAPTER 2 Pyrometallurgy I: Roasting—Agglomeration—Caleination Minerals recovered from ores ate not always in the optimum chemical or physical state for conversion to metals. Oxides are more conveniently reduced to ‘metals than sulfides, or the metal might be more readily leached feom the ore if it ‘were present as a sulfate, a chloride, or an oxide, Chemical conversion to the desired Species often is an integral segment of the extractive process. Sulfide ores, for example, usually are heated in an oxidizing atmosphere (roasted) t convert them to-an oxide or sulfate. “The physical state of an ore may be foo fine for charging toa provess. Fine ores often are agglomerated by sintering prior to charging to a blast furnace, the prin- cipal smelting unit for lesd and iron. In the ease of iron ore, pelletizing, another very Important agglomeration process, recently has achieved commercial adaptation in the iron and steel industry, Pelletising is © process in which iron oxides fines frst are agglomerated into small pellets that are then fired to produce a small oxide Driquet suitable for charging to the iron blast furnace. In the following sections, several commercial techniques for roasting end agglomerating ores are discussed. In addition, the thermodynamics of sulfate rosst- ing is considered. and the thormodynamics and kineties of calcination are presented. 2-1 Roasting of Sulfide Ores ‘Many important metals, including copper, leed, and zine, occur in nature as sulfides. In early sivilizations it’ was discovered that heating sulfide ores in air converted them to a form whereby they could easily be reduced by charcoal to a metallic form. In modern industrial practice, with a considerable amount of fine material being produced in various concentration operations on low-grade ores, several types of roasting equipment have been developed. Roasting is carried out by rabbling over a tier of hearths in » multihearth roaster, by expasing the sulfide ore to oxidizing gasos in a shower roaster where the ore falls through hot gases, in fluidized beds, or by ‘exposing the ore in a packed bed to a controlled flow of gas, as on the Dwvight— Lloyd sintering machine. The conditions of roasting determine whether or not the sulfide ore is partially roasted to a sulfate or completely roasted to an oxide, ‘Thermodynamics of Roasting Reactions A number of reactions take place during the roasting of sulfides. Overall reactions using the roasting of galena (PbS) as an example are given inthe following ‘equations. In addition, several other intermediate reactions ean oceur involving. the oxysulfate of lead, 78 Unit Processes of Batractive Metallurgy Most roasting is earried 10 completion (so-called “dead” or “sweet” roast) with elimination of most of the sulfur by the overall reactions 2PbS + 80; = 2PbO + 280s, (ay Similar reactions can be written for zine, copper, and iron, At lower temperatures, sulfates can be formed: 2PbS + 40, 2PbO + 280s + Os = 2Pb8O, 3) 2PD80,, (22) At higher temperatures, the oxide can be reduced by the sulfide to produce the free metal, BPeO + PAS = SPb + 80s ea Control of temperature and oxygen potential (pressure) can be employed vo produce the desired oxidation state. In the ease of concentrated zine ores that Inter are soing to be reduced with earbon, an oxidizing roast with elimination of as much sulfur as possible is desired, fn the ease of a copper ore which is to be leached, the ‘objective is the formation of as much water-soluble sulfate as possible. In considering the thermodynamics of roasting, it should be noted thet sulfur trioxide is formed in the ges phase according to the rexetion, $0: + 10; = 60s ‘This reaction is favored at lower temperatures. Oxide-sulfate equilibria can be ‘considered in the form, MSO, = MO +80, (28) ‘where M represents a metal ion. These equilibria could also havo been treated in a form obssined by combination of Eqs. (2-5) and (28), as for example, in Eq, (2.3), where the equilibrium eonstant* would be expressed as Kom iPaoiPon on Standard free energy relationships for several sulfation equilibria of this form are summarized in Table Ac (see Appendix A) ‘The metal-sulfde equilibria ean slso be presented as oxygen-sulfur dioxide equilibria with the chemsesl reaction written MS + O: = M + SO:. (2-8) The equilibrium constant can be written inthe form, anPeos os) ausPor ee Ke “An understanding of physical chemistry has been presumed, including thermodynamics, ‘hes eli, and elementory Kinetic, Purometallurgy I: Roasting—A gglomeration—Caleination ° ‘Then for pure solids in theit standard state at unit activity log Poy (210) ‘The thermodynamics of sulfate systems thea eam be presented conveniently in terms of predominance area (log Psoe versus log Po.) diagrams, Pree energy data, for oxide and sulfide systems are requited to determine relations of the form shown in Eq, (240), of for Eq. (2-7), where for unit activity of the solids log Peoe = —Hlog Ks ~ $106 Pos ey A predominance ares diagrem (or thenickel-oxygen-sulfursystemis presented in Fig. 2-1 for a temperature of 1000°K. The small square in Fig, 2-1 enclases an area ‘where the oxygen and sulfur dioxide pressures range from 10-10" atm. In opern- tions at 1 atm total pressure, gas compositions from 3-10% oxygen and $-10% sulfur dioxide would yield nickel sulfate as the stable solid phase. At a gus phase log Pos = log Ke vo00%« “Ze Te me za m4 ° 106 Poy Fig. 2:1, Predominance Area Diagram fof the NiS.O Syatem ot 1000°K Source: T-R Ingraham, “Suiphate Stability aed Thermodynacnie Phase Diagrams with Parti luz Reference to Routing” Aplications of Pendamantal Thormodajomieso Metalrycat Froctts, Gordon and Breach Sennen Publisher Tne, New York, 26T, 9.1810 Unit Processes of Ratractive Metallurgy composition of 1% oxygen and 1% sulfur dioxide, nickel oxide would be stable, At the univariant point of Fig. 2-1 (Psoy = 2.5 X 10 atm and Por = 5X 20> stm), the required conditions are so reducing that itis unlikely that metallie nickel vould be formed in commercial roasting operations. The influence of temperature ‘on these equilibria uso ean be employed advantageously to produce a desired end product by shifting the loeation of the predominance areas, Sulfide concentrates of copper and cobalt are sulfated in « uidized bed opera ton at 950°K to produce 87% soluble eopper and 93.5% soluble eobalt. The rosster gases analyze 8% 80s and 4% Ox. Predominance aren diagrams for copper and cobalt at 950°K are superimposed in Fig, 2-2. The point representing the commercial ‘operation for roasting eopper-cobalt ores is shown to lie well inside an area where C080, and CuSO, are stable. If a separation of copper and ecbalt were desired in the leaching operation, a roasting operation in “area A" of Fig, 2-2 would produce 100 Pep Fig. 22. Superimposed Predominance Digrams forthe Co-S-0 and CuS.0 Systeme ot 980° Source: TR. Ingraham, “Sulphate Stability and Thermodyosmic Phase Dingrams with Partcule Reference t9 Roasting” Applications af Pandomenal Thermosyeamce (0 Meallrpcal Pras, Gordo. apd Breach Science Publishers Ins, New York, 1087, Pyrometallurgy I: Roasting—Agglomeration~—Caleination un valer insoluble cupric oxide and soluble cobaltous sulfate. This seperation ean be rade on a commercial seale. Exanple Problem 2-1. A lead roasting operation at 1100°K is proposed with 12% SO, and 4% Os in the roaster gases at 1 atm total pressure. Is lead sulfate the stable solid phase? With 1% Os in the gas, what partial pressure of SOs is necessary +o form the lead oxysulfate PbSO,-PLO? Solution. At L100°K the equilibrium constant for the resetion 80: ~ $0; + 10s, (a) PeosPoo og (os) Pao With Pros = 0.12 and Poy 04, the effective pressure of $0s is (6.12)(0.04)* 1 0.0155 atm, (20) Pao ‘This pressure then ean be utilized for eomparison with the SO, pressure determined for the equilibrium -2PbSD, = PPSO,-PbO + 80s (2a) From Table A AG), = 74000 + 16.81 Tlog 7 — 97.4 T (2) Av 100° GY, = 23,060 eal/mele log Ka = log Pro = —4.58, Pooy = 268 X 10 atm ‘This partial pressure of SO, is well below that existing in the toaster gases, and, hence, PbSO4 is the thermodynamically stable phase. TE the gases contained 1% oxygen, using Eq. (2-b) the partial pressure of SOs in equilibrium ith PbO, end PbEO,-PbO would be (U.58) (263 x 10-4) Oar = 897 X 1 atm Lesd has an extremely strong tendency to reaet with sulfur, This tendeney is such, that even a trace of SO: (Psoy = 10"tutm) in a Dlase furnace gas is suficient to sulfatize PbO ¢o PbS0,-PbO Furthermore, the thermodynamic stability of lead sulfates makes it extremely digicult to decompose them to the oxide. Tn addition to the complications arising in copper, lead, and zine processing because of the possibilty of forming of oxysulfates, it should be noted that gangue material present in the concentrate charged to the roaster also may react to form ‘complex oxide compounds. This would reduce the activity of the copper, lead or zine oxide, and coreespandingly reduce the equilibrium partial pressure of SOs LER Theya, J. Atta 10, 45 (1058),2 } Unit Processes of Extractive Metallurgy Volatilization During Rossting ‘The roasting of sulfide ores permits, in addition to the conversion of sulfide to oxide or sulfate, the vaporization of volatile compounds. In perticular, antimony and arsonie are found in appreciable concentrations in flue dusts from the roasting ff charge materials that contain only traces of these metals, The trioxides of antimony and arseni, formed by heating the sulfides in air at temperatures as low as 400°C are sublimed in the later stages of roasting. Zine and eadmium when heated under reducing conditions are vaporized (see Pyrometallurgy Il). ‘A ehloridizing roast in which salt (sodium chloride) is mixed with the sulfide ore charged to the roasting operation etn result in & conversion of iron, silver, lead, and copper to chlorides that are readily disolved in water. Such a conversion to chloride is facilitated by the presence of earbon, Far example, tin and tungsten are partially separated by roasting in an atmosphere of chlorine and hydroehlorie acid AL 600°C the tin and some of the tungsten are volatilized, and at higher tempera tures the remainder of the tungsten, and iron and manganese, come off as chlorides. ‘The presence uf reducing agent such as earbon can markedly lower the tempera~ ‘ure required for this type of reaction. Far example, chlorination of magnesium oxide is carried out at 1000°C in the presence of eoke aecording to the rexetion MgO + © + Ch(g) = MgCh(s) + CO. (212) HCI gas also ean be used to convert some metallic oxides to chlorides by a reaction fof the form, MO, + 4HCI = MCL, + 2,0. 3) 2.2 Industrial Roasting Processes As mentioned previously, roasting is carried out not only to render the material ‘chemically suitable for a subsequent processing operation, but also to provide a suitabie physical state of the material. In the eace of eopper and ather metals that are smelted in reverberatory furnaces, the roasted material (ealeine) should be finely divided, whereas in biast furnace operations for materials suck as iron and lead, the ealeine must be ina reasonably large agglomerated form. Several processes are available for providing these conditions. The important industrial techniques for roasting are mechanical roasting, fash tossting, fuidized bed roasting, and blast o ‘Mechanical or hearth roasting is carried out in a vertical multihearth system in ‘which 8-12 hearths are enclosed in a large cylindrical shell 20-26 ft in diameter and 30 ft high. A sectioned view of this type of roaster is shown in Fig. 23. The ore fenters at the top and drops from hearth to hearth while the sulfide ore particles are roasted as they come in contact with the rising gases. The veseel is ined with fire briek and is equipped with e rotating rabble attached to a central shaft that serves to move, or rabble, the ore across each dise-shaped hearth, The oreis plowed toward fan opening on the outer or inner edge of the hearth where, in tura, i falls to the hearth below. The rotating rabble arms are cooled, and openings are provided in the shell for ease of maintenance. This type of equipment ean roast from 100-200 tons Pyrondainy T:Rotng—AaslomarionCalnaton ts wo aa Q@ ¢ sn Hs mm omy, ey tise an sae | WITH BLADES «ROASTING aie ROASTING am =) toasts i ou 2 eonge Of B cute ve D Fig. 2-8, Moltipie Hearth Roasting Furnace Source: Lurpi Manu, Lurgi Gesllachattn Frankfurt (Main) Germany, June 1861, p22. of material por day. Heat ean be supplied by combustion of fuel, but usually the process is autogenous, that is the oxidation of the material is sufficient to supply ‘thermal energy to the system. Flask roasting is a moditcation of the multiheurth roaster, After it was observed that the oxidation occured on the surface of ore exposed to the roasting gases and, in particular during the period of fll from hearth to hearth, flash roasting was developed. This process is carried out in @ unit similar to & hearth roaster except that several intermediate hearths aro removed. The concentrate which often is wet is dried on the first upper hearth ot tio and then falls through a combustion chamber. After sotting on the lower hearths, the caleine is collected end discharged from the unit. In the ease where combustion is nat autogenous, auxiliary fuel is borned in the unit to maintain the process temperature. To provide for conversion to sulfate inthe ease of zine rossting, additional amounts of SO: are often added to control the atmosphere on the lower hearths. A cross-setional view of a flash roaster for processing zine concentrates is shovsn in Fig. 2-4Pyrometallurgy I: Roasting—Agplomeration—Caleination 16 Pluid bed roasting has been developed since World War TI and is now widely weed for roasting iron sulfide, and in several instances the sulfides of eopper, cobalt tnd nickel. A sehematie diagram of a fluidized bed system for rossting sulfide con- ‘enteates is showin in Fig. 25. ‘The most important variables in the fluidized bed are the particle diameter, or average diameter, and the superficial gas velocity. Figure 2-8 shows the relation- ship between particle diameter and superficial gas veloity for Buidiaation at @00°C, It should be noted that because of interaction between the solid particles in o fuid- ined bed, particles which are fine enough to be carried out of the bed and particles which are coarse enough to sink through the bed may exist in the fuidized state. Fy EE Consequently, within a resonable range of particle size, the average diameter may = be used to characterize the behavior of tha bed. os Hl g ‘Temperatures in the fluidized bed ean be controlled by proportioning the ~ relative amounts of feed and air. Once initiated, combustion in the bed is solf- _\ sustaining and a continuous supply of air and feed is provided to the roaster Fig. 24, Suepenson Roaster for Routing Zine Concentrates, Tal, British Columbia Sourse: Stel eta, ASME Tron, 1896, Vol 21, p. 542. BOASTING AS Tous ce noastee un own rire s Waste Far goueR reuent aver see ooune con's e 48 ovearion our rie oasting, “inocR cOOLING ORUM ool 1101001000 Fig, 26, Gas Velocity—Paticle Diameter Relationship for ludatin at 900°C Fig. 26, Fitioed Bed Roaster Souree: R. B. Thompson and G, Rosser, Eeactie Metaturgy of Copper, Nickel and Cobb Source: Lary Monuol Lrg Geselchaten, Frankfurt (Main) Germany, June 1981, p. 195 AINE Serposien, New Yorks Tnterece Bass Tne 8, 0s &16 Unit Proceeses of Extrastive Metallurgy 4 Fig. 27, Dwight-Liyd Sintering Machine Source: Larpi Monuel, Lurgi Genlsshaten, Frankfurt (Maia) Germany, June 181, p. 180, Sinteroast offers an advantage over the previously deseribed roasting pro- ‘esses in that agglomeration of the roasted material is accomplished. The blast furnace requires a suitably large particle size, and hence iron end lead sulfide ores are sinterousted. TThis process is usyally eartied out on a Dwight-Lloyd sintering machine, as shown in Fig. 2-7. Roasting is aecompanied by incipient fusion, which produces a porous cinder-like material called sinter. ‘The Dwight-Lloyd sintering machine, shich was developed more than 50 years ago, consists of a series of pallets or grates mounted on an endless track. ‘The concentrate is charged to & depth of about 6-20 in. on the pallets, which move over wind boxes at 2-3 ft/min. Combustion ofthe bed is initiated on its surface by burner, and the combustion is maintained and carried through the mass of the charge by the air drawn through the concentrate to the wind box below, which is connected to a suction fan. Relatively high temperatures (900-1200°C) are de- veloped in the material, causing it to fuse into a compact mass. After the sinter has reached the end of the machine it is discharged, cooled, and sized to provide a ‘uniform product. Fines from the sizing oeration are returned as charge material In sintersogsting, the sulfur in the ore acts as a fuel. The relatively high temperatures and oxidising conditions usually provide low sulfur eontents, particu larly for the roasting of pyrite (FeSs) or pyrrhotite (FeS). In the case of low sulfur or oxide ores, fuel is added. The latter ease is referred to simply as sintering and is used in particular for preparation of charge material to the iron blast furneee 2.3 Sintering ‘The requirement for course charge material for the blast furoace necessities aeglomeration of fne ore One method for agglomeraing fines is by sintering sFng i the proses of heating ne materials to an elevated temperatare without ‘ample fusion such that the ema, solid particles ic contact-wih one a fudbore and agglomerste into larger, more seul particle ‘The predominant ‘Mechanisms in the action of sintering are surface diffusion and incipient fusion, and both acer inthe commercial sintering of oe “The sintering of large quantities of material is often necessary in the operation Pyromaalturgy I: Roasting Applomeration—Caleination x of a metallurgiel plant. This process provides an opportunity to use fine material, fnd often makes @ particular process feasible by converting available fine materials to-an agglomerated form for use asa charge material. Sintering is sometimes eartied ut in rotary kilns or by batch processing on sinter pans or hearths. Flow of air thraugh the charge may be by updraft or downdraft methods, but the predominant industrial technique for sintering ore is on @ moving hearth, as with the Dwight Lloyd continuous sintering machine, As originally designed for processing copper ores, the sulfide fines were distributed in a thin layer along a treveling belt made up of grates, The charge was ignited and the sulfur burned out of the ore as air was dravin through the charge by large fans. The fines fused together, forming a strong sinter eake that was desirable for charging to a blast furance. The basic difference between the processing of sulfde ores and the sintering of oxide-fertous ores is the self-contained fuel of ce sulfide material. In the processing of hematite or magnetite fines, carbon in the form of coal or coke has to be added to provide fuel for the sintering process. “The utilization of the Dwight-Lloyd machine (Fig. 2-7) in the processing of iron ores is essentially the same as for nonferrous sulfide ores. A schematic diagram. of an iron ore sintering plant is shown in Fig. 2-8. It is evident that an important part of the sinter plant is the mixing system that blends the fine ores, limestone, coke, plus the fines returned from the sinter strand. The charge mix is loaded onto the moving grates of the sintering machine, where it passes under # burner that ignites the bed. Airis drawn through the burning bed by the suction system below, Fig. 28, Tron Ore invari Plant fr Proparaton of Sel using inter Sour: Lurpé Manual, Lurai Gewschaten, Frasklurt (Main) Germany, June 1961, p. 18.18 Unit Processes of Bztractive Metallurgy and ot the end of the strand the sinter drops off the pallts, where itis evoled and terete. The underize parties ate then retumed to th sintering proses as ‘The fuel requirement for the sintering of iron oxide ores ranges from 5-8% ‘coal or coke, and is relatively independent of the material to be sintered. The optic ‘mun for the fuel requirement varies slightly and depends upon whether or not chemical resets are involved inthe sintering process. The presence of appreciable amounts of limestone or water will sequire additional fuel, and may depress the maximum temperature achieved. Variation in the carbonate oF moisture content of the sinter mix will give a variation in the width of the hot zone that moves down, through the ore bed. In normal downdraft sintering, the combustion of the fusl in the sinter mix is initiated in the upper levels of the sinter bed, Te hot combustion ‘gases are pulled downward through the bed and preheat the sinter charge. The presenee of water in the sinter sx will imit the inerease in temperature of the sinter bed until the water is vaporized. The presence of carbonate, such as limestone that is charged to seli-luxing sinter (seo Pyrometallurgy IID), will result in a ‘broadening of the combusion front that follows the heat front dovin through the bed ‘aaa Sine Oar er epee Conti a Fig. 20, Tempersare Distebution fr Two Sintet Mixes (Combustion is oecrrng approximately atthe midpoint of te bed) sta kt: STEBLAFARING, The Chipman Coneree,-180 MET Pe, Cas, ‘Pyrometallurty I: Roasting—Agolomeration—Caleination 19 Figure29 shows the infuence of the presence of a large amount of ealeium carbonate in the charge. The peak. temperature of the bed is decreased and the width of the hot zone is increased. A well-defined planar front should occur in sintering, as ilusteated by the solid lin in Fig. 2-9 "The engineering relationships for design of sintering operations are based on flow of ir through porous beds. OF particular importance is the bed permeability, hich Sften can be determined by laboratory sintering tests* In commercial operations, 1 to 3} tons of material can be sintered per square foot of hearth area per day. on & Duight-Lloyd sintering machine. A decrease in ful requirements could be achieved through the use of preheated air supplied from a closed hood over the sinter strand, Up to 40% of the thermal energy required for sintering can be supplied by fuels such as flue gas, natural ges, oF fuel gil burned in a hood above the sinter machine. With this "mined firing process,” the mechanical and chemical properties of the sinter ean be improved* Control ofthe sintering of iron ores by the Dwsight-Lloyd process is of particular importance as the productivity of the iron blast furnace inereases. The control of inaterial fow and suitable proportioning of raw materials to provide a chemically “uniform sinter mix is of prime importance. Maximum utilization of the sinter strand requires control of the "burn through" point suck that combustion is completed. Just as the sinter reaches the discharge end of the strand. The temperature in the ‘wind box often ean be used to monitor this “burn through” point. 2-4 Palletizing Plletizing is recently developed agglomerating process for iron ores that has made possible the economic utilization of low-grede taconite ores. The use of pellets fr blast furnace charge hss resulted in mated increases in blast furnace produc- tivity (see Pyrometallurgy IIL). Tsconite is an intimate physical mixtare of ragnetite or hematite with gangue materials, Successful separation ofthe iton oxide from the gangue material requires crushing and grinding to extremely fine particle snes, The agglomeration of this material has been successfully accomplished by balling the ore in various rotating devices auch as discs, drums, cones, ete. and once the fine material is balled, it is hardened by heating, generally referred to as in- urating. A schematic diagram of a pelletizing plant is shown in Fig. 2-10. During induration, several chemical reactions occur, including vaporization of free water, vaporization of combined water, calcination of any limestone present, and in the cease of a magnetite (FeiO,) concentrate. the oxidization of the magnetite to hhematite (Fex0,). Laboratory tests are ususlly employed to determine the optimumt time-temperature pattern for induration. The final temperatures during induration reach 2300-2400°F, depending upon the concentrate being pelletized. Shaft fui neces, kilns, and traveling grates with updraft or downdraft techniques are used © 2B, W. Voice, Brooks, and P.K. Gleb, J 1.8.1 16,196 SELW. Voice and R. Wi, J. Metts 10,105 (1958) + busy! Manoa p 150, ri Geolscheften Frankfurt (Main), Germany, June, 1961 ‘A Bragaed, J, Malle 19, 9-37 (987) 3)it Processes of Extractive Metallurgy ee Journ, ae om 1) | to ames 128 SH A yer nN | a ow! ne ee Ase — as sr wat Goer (Fate vers Fig. 210 Paletising Plat Flow Disgram > Source: MJ. Greaves and A. English, Agglomeration, New York, Intrecience Publishers, 1982 pi, fire the pellets, Peletiing machines are designed for producing between 2500-3000 tons of pellets per day and designs are being prepared for machines eapable of producing 5000 tons per day. A typical balling drum circuit, in conjunction with shaft furnaces for indurating the pellets, is shown in Fig. 2-1. Wich a suitable amount of moisture and a binding agent, usually a elay such as bentonite, the finely divided material is rolled on an inclined drum, dise, ete, eausing the ore particles to eling together and rol up into small spheres. The material discharged from the balling unit is sized, and the under- sled pellets are reeyeled. Limestone often is added to provide a fluxing agent during subsequent smelting in the blast furnace. Other techniques are available for indurating the pellets, including the hori- zontal grate shown in Fig. 2-12, A recently designed pelletizing process employs & traveling conveyer for drying and initiating induration, a rotary hearth furnaee for raising the temperature of the pellets to 1200°F, and an indurating stove ot shaft, furnace where the reaction from magnetite to.hematite is accomplished by a eon trolled flow of sir through the packed bed. The stove includes both a heating and ‘eooling section, The system is shown schematically in Fig. 2-18. Automatic control of the pelletizing plant, utilizing bed-level control, temperature controls, pressure ey Pyrometallurgy I: Roasting—Agolomeration—Caleination en conttols, and Mow instruments ia eonjunetion with a digital computer, is being, {installed fn several locations. "The rapid development of pelletizing plants on the North Ameriean continent stemmed from the need for tresting fine size maguetite concentrates produced from taconites of the Massabi range, which could not be sintered successfully because of their extreme fineness, The advantage of this process is such that the bulk of the iron ore produced in North America is now being pelletized. High-grade ores mined underground are also being directly pelletized, and consideraticn is being given to partial reduction of the pellets during induration, whieh could lead to even higher produetivities for the blast furnace. Fully reduced pellets are being prepared for direct charging to steelmaking furnaces. Fig. 2-11, Typeal Shaft Furaase elletising Plant Source: A. Baglsh and M, J. Greaves, Soe. Mining Bginering Tronsetions, September 196, p aosUnit Processes of Eatractive Metallurgy Fig, 2.12, Horizontal Grate Peltising Plant of Reserve Mining Co, with Milion ton per Year ‘Capasty, Magnatite Concentrate Sours: A, English and ME J. Greaves, See. Mining Brgincere Trontacons, September 1953, 0. 2-5 Caleination Cleination of natural carbonates yields ime and magnesia whieh have long been important materials in the metallurgical industries. The major tonnage outlet for ‘magnesia is as the refractory ‘dead-burned grain magnesite.” Lime is also a refrac- tory material, but eannot be uted in commercial seviee. Exposure to the atmosphere after calcination will result in reaction (slaking) with the water vapor in the sir, thus rendering the lime useless. The use of lime as s neutralizing agent for acid pickling and leaching solutions is well known. The use of lime as a @ux for oxygen steolmaking has markedly inereased the lime consumption in the steel industry, replacing the limestane previously used in the open hearth process. Calcination of limestone is carried out in many types of kilns, including rotary, shaft, and rotary hearth ‘Thermodynamics of Caleination ‘The reaction that occurs in calcining © chemically pure limestone may be expressed as| CaCO, = CxO + CO, ea) Pyrometallurgy I: Roasting—Agglomeration—Calcination 2 Fig. 248, Heat proous ggupment (in which grtn balls of magnetite or ae loaded onto ste, dryer conveyor and died aad prabested at temperatures upto G00°F in ait.) Souroe: 1, W. Smith, D. Beggs, and ¥. G. Rinker, J of Masa, 1986 Vol. 18, No.9, p, 1022 ‘The equilibrium constant for Bq. (2-14) is Ku = Poor (248) ‘The free enssky of decomposition may be exprested asa function of temperature as AG? = 42,400 ~ 37.7 7 = —4.575 Tog (Poos) (210) Fquations (2-15) and (2-16) ean be utilized to calculate the equilibrium pressure of COs in contact with hested limestone, Kinetics Mechanism of Caleination In addition to predicting the temperatures st which decomposition of the limestone can take place, it is necessary as well to consider the kinetics of the reaction, Although several experimental investigations have been made to elucidate the exact manner in which the decomposition takes place, little suecess has been. obtained in defining a mechanism for ealeinstion. It has been found, however, that calcination of limestone takes place at a definite boundary plane, ie, the bounda of two solid phases, one of lime (CaO) and the other of limestone (CaCO.). This plane progresses from the surface of the piece of limestone being ealeined toward 0, Kubasshewi and EL. 1066, rans, Meallurgial Phrmochemisty, John Wiles, New York,2 Unit Processes of Extractive Metallurgy the conter at a definite rate and is maintained in about the same shape as the external surface of the stone. Based upon calcination data, Furnas derived the following equation, which can be used to determine the progressive penetration of the zone of eslination: log R = 0.003145 7 — 3.2088, (ary where R = rateof advance of otleination interface, om/r, T= temperature of surroundings, °C. Assuming thatthe heat absorbed by the limestone is proportional to the surface trea of the reveding interface, a constant rate of advance of the interface is pre- icted, If the rate of movement ofthe interface is dependent ly upon temperature and available area and is independent of size and shape of the particle, the time required to caleine is directly proportional to the size of the piece. Conley? Pelilke ‘and Kim, and others have demonstrated the validity of a constant rate of advance of the calcination interface, although the rate equations vary with the particular stone under study. Thus, in operating practice, it is necessary to evaluate the calcination behavior of a material before specifying operating conditions for a calcination process, Bibliography Davis, E. W.. Pioaering with Taconite, fineaota Historical Sciry, St, Paul, Minn, 1964 ‘Greaves, M. J and A Bgl Bagiwerngcontcibtion to new ac ique of iron oe egglomert- ‘on, Agglomeration, pp 419-48, Interesionce Publier, New York, 1002 Hopking, D. W, Phyotal Chantry and Mot! Extraction, The Mactan Company, New York, 1, [alogs, H. HA critical review of sulfation exuliria, Trane, Me. Soe, ATAUE 230, 1622-1834 (1068), Leva, Mas, Fiction, MeCran-Hil, New York, 1939. Newton, 1, Extractive Bitar, John Wiley, New York, 150 Roberts JP Mecha of unering, Metra 42,15 (1950) Smith L- W. D. Boge. hau FG. Ricker, A new procs for oxide pellet production, J. Metals 18, 10a1-1006 (186 ‘Thompson, R.B.and G. Rowner, Fluid bed rsstng-principles and practice, Bvacto Mellurny (of Copper, Nik, and Cob, ALME Syrnpesum,Intreienee Publabers, New York, 196. Voiee,E. W.,8. H. Brooks, W. Davies and B.L. Roberton, Sompariom on Sine, Special Report ‘No. 58.45, Ion and Stel Inatiite, London, 1955 Voice. FW. std R. Wid, The nfuence of fundamental actors a te star proves, Sintering ‘Sompoeium, Australian Test. Mining and Mot. Port Pie, 158, Discussion Questions A. The sinter-sousting of fine nickel sulfide (—200 mesh) has several inherent disadvantages. Its low melting point favors fusion on oxidation, producing a #0. Farms, Ind Bop. Chem. 25, 594 (1991. +4. E. Cony. Technical Publication Number I0W7, Mining Tech 3 (1930), ‘SR D, Petike and Y.U. Kim, Private communication, The University of Miah i t ' Pyrometallurgy 1: Roasting—Agglomeration—Caleination 2% relatively dense product which is insufficiently sative for gertain subsequent processing operations. Suggest © process which will result in a mote acceptable product. y 2. Discuss the economic factors whieh determine the optimum length for a sinter strand. 3, Summarize the preliminary procesting steps for the principal ores of the common metals , 4. Contrast the advantages and disadvantages of sintering and pelletizing of ian oxide fines 5, What are the relative merits of the shalt kiln, rotary kiln, end rotary hearth furnsee for calcining lime? 6, Diagram the steps involved in concentrating and agglomerating taconite ores, 7. Describe various gas treating systems employed to control the sulfur-bearing ‘gases from roasting operation: Problems 1, Nick! sude roasting i carried out at 1 atm total presse and 1000°K with 8 phe compositions in the ranges 3-10% Os and §-10% SOs, Over what Potion of these composition ranges i nick! sulfate the atable phase? 2. Sulfide concentrates of copper and esbalt are sulfated in sAuiined bed opera- vion at 950°K and ner I atm pressure to produce 977 soluble eopper and 7 soluble cobalt. Roaster asta are reported to analyze 87 SOs ana 8% O2, Was far-sold equim reached in ths system? 3. Copper and cobalt sre to be separated by rosting at 1 atm and 950°K to produce water soluble eabsltos sulfate and water ingoluble cupric oxide. Recommend a contrl point for roaster gas composition 4. Roasting of sphalerite fs being carried outst 1500°F and at an average roster {538 composition of 10% SOs and 47 Os, The reultng cline is basi ulate (Zn0+2Za80,). How would you change the ges composition and/or tem perature ta produe a ealeine of (a) 200 72804 5. Fvaluste the thermodynamic feasibility of roasting to a sulfate and to an ‘oxide for separation in a subsequent leaching operation for sulfide ores con= ‘ining (2) iron and copper (b) iron and zine (c) zine and cobalt (€) nickel and copper Specify roaster gas compositions if separation ean be accomplished.By 10. Unit Processes of Extractive Metallurgy Calculate the maximum pressure of SO; at which Ph and PbO can coexist at 1100°K under equilibrium eonditions ((e., without forming the lower sulfate PLS0,-4PD0). Consider the fluidized bed sossting of nickel sulfide at 2000°P and a rate of 1 ton/br. Given: 136 £0" GTP) of roaster gas (Ns, Os, 80:) per pound of sulfide, ‘The product contains 0.5% 8. Heat losses equal 850,000 [Btu/hr. Sensible heat of product equals 400 Btu/tb Ni Compute: (a) The heat evolved by oxidation of the nickel sulfide (lb) The excess air which is required to uidize the bed (c) The pereentage of thermal energy whieh is retained in the exiting roaster gas. tis desired to produee @ feed for electzo-winning of copper from a sulfide ore using a fluidized hed roaster. Specify the required operating temperature of the resetor and the composition of the exiting gas stream, Cee Component Composition (wt %) Copper (as sulfide) 48 Iron (as sulfide) n Sulfur (as sulfide) aL FLO, free and combined 3 COs, as carbonate 3 Inerts, SID, ete 2 ‘The oxidising gas is 10 moles of sir/mole of copper supplied to the roaster. One hundred pounds of ealeium carbonate is stored in a sealed canister with a volume of 5 10. The eannister is heated to 800°C. (a) What is the pressure of COs at equilibrium? (b) How much CaO would be formed at equilibrium? Specify operating conditions for a large rotary kiln calcining 1-in, pieces of limestone, CHAPTER 3 Pyrometallurgy I: Oxidation-Reduction Reactions 3-1 Thermodynamic Stability of Mineral Compounds Less resotive metals, including gold, aver, copper, end the platinum metals, are sometimes found in aature in the metallie state. Most metals, however, are usually ound as mineral compounds such as oxides, sulfides, earbonates, or silicates; the mineral may be a single eompound or it may be a physieal mixture of « number of compounds. As outlined in Chapter 1, a combination of several separation or con- centration processes are employed in the extraction of metals from their ores. When further concentration eennot be earried out by physical means, chemical separations must be employed. The conversion of sulfides to oxides by roasting or conversion of earbonates to oxides by calcination are typical pyrometallurgieal processes designed to modify the minerals of useful metals to a more easly separable form. ‘Theease with which a metal can be recovered from its mineral form can be evalusted quantitatively in terms of the thermodynamic stability of the mineral eompound; consequently, some attention shuld be given here to the nature of various mineral compounds, ‘Thermodynamie Stability of Oxides ‘The practicality of chemical processing for the extraction of metals ean be assessed on the basis of free energy changes for the reactions involved, a negative free energy change indicating that the reaction will tend to occur. The frst step in evaluating the free energy change isto determine standard free eneray changes, A. convenient means for comparing free energy changes occuring in various chemical reactions is to display them graphically. One useful chart, iret proposed by Elling hham,' is a plot of the standard free energy of formation versus temperature for {8 group of compounds of a given type, eg, oxides of various chemical elements, ‘This chart indicates the relative tendeney toward oxidation for these elements and shows directly conditions under which resetions oeeur, thus providing ® basis for evaluating the possibility of chemical separation by ‘an oxidation-reduction re- ‘ction. The Flingham diagram showing the standard free energies of formation of oxides asa function of temperature is presented in Fig, 3-1 ‘The free energy-tempersture relationship shown in Fig. $1 is nearly linear. ‘The apparent linearity is the result of heat capacitis of reactants and produets being essentially equal. The slopes of the plots on the Ellingham diagram are SH... Bllingham, J, Soe. Chen. Ind. 63, 125 (1944 m2 Unit Processes of Estractve Metallurgy ++ m0 eens « urea zt Fig, 24, Free Bnargy of Formation of Oxides Source: H. J. Elighatn, J: Soe, Chem, Ind, 1044, Vol 68 p. 197, Society of Cheon Tae dusty defined by the well-known thermodynamis relationship (aagn °, (Bl (22), = -as en Pyrametallurgy II: Oxidation-Retution Reactions 29 change, IF the entropy’ change oeeurs in the reactants, the inotease in entropy by a phase change, e.g., solid to liquid or liquid to ges, increases the entropy of the reactants and results in a more negative entropy change for the reaction. In cases where the product shows a phase change, wth en accompanying inerease in entropy, the slope ofthe line decreases in a corresponding manner. Standard free energies of formation at high temperatures for several reactions of metallurgical interest are ‘summarized in Table A-II in the form of equations that are linar with temperature. ‘The standard free energy change for an overall reduction process can be cal- culated by eombining free energy changes for the individual oxidation-reduction reactions involved. Consider the two reactions, 2Mg(g) + Ox(a) = 2Mg0(8), (32) Si(s) + Ox(g) = S036) (33) ‘The standsrd free energy change for the reduction of magnesium oxide by silioon can be determined by subtracting Eq. (3-2) from Eq, (3-3) to obtain 2Mg0(s) + Si(s) = 2Mg(g) + S10.) ‘The standard free energy change is given by the difference between the standard free energy changes for Eq, (8-3) and Eq, (3-2), ie., Gs = aGy — Ge 35) 4) fears pelt of The Sym BaD Fig. 82, Equilibrium inthe Syatem 20.0 Source: MJ. N. Poupbalt and C. Mf Rorive-Boute, Die. Faraday Sie, 1048, Vol. 4, p. 142, Butterworth and Company (Publ) Eid0 Unit Processes of Extractive Metallurgy ‘This reastion forms the basis for the Pidgeon process for the production of mag- Pourbaix? proposed another form of diagram for treating phase equilibria in oxide systems in whieh he plotted the logarithm of the equilibrium oxygen pressure ‘against reciprocal temperature. An example of a Pourbaix diagram for the zinc~ oxygen aystem is shown in Fig. 8-2. The lines on Fig, 3-2 represent phase equilibria between zine oxide and zinc in solid, liquid or guseous form. The phase equilibria, are shifted by pressure, and this is indieated by the vertical lines, whieh show in- creasing aine vapor pressure with increasing temperature. Figure 3-2 shows that heating aine oxide to high temperatures will result in thermal dissociation, de- pending upon the partial pressure of oxygen and zine, according to the reuctio, 2Un0(8) = 2an() + Onle) (3-6) If sine oxide desomposes under high vacuum conditions wherein the pressure of zine is twice the pressure of oxygen in the atmosphere as shown by eurve (g) of Fig. 3-2, 40 Toz05,6 Rx cots) WKS & 120 -RT to Po, (heal) 160. 2005 1000 2000 2800 Temperoture (°K) Fig. 3, PourbaicElingam Diagram forthe Ta-C-0 Systm Source: W. L. Worell and J. Chipman, Trans, Me. Soe. ATM, 1964, Vol. 20, p. 1084, LM. Bidgoon, Trans Canad. Mon. Tat. 495 621 (1948) SMA. Poul, Bal Soc: Chim. Bal. 8, 145 (194. Pyrometallurgy I: Oxidation-Reduction Reactions 3 the decomposition pressure or total pressure in the system reaches 0.01 atm at about 477°C and 1 atm at about 1962°C.+ ‘A very wseful equilibrium phase diagram can be derived by combining the concepts of the Ellingham and Pourbsix diagrams. This is illustrated in Fig. 3-3, 4 Pourbaix-Ellingham diagram for the tantalum-earbon-oxy/gen system. In Fig 3.3, the near linearity of the Ellingham diagram and the description of phase ‘equilibria ofthe Pourbaix diagram have been combined by plotting versus tempera~ ture the standard free energy of decomposition of the phases in equilibrium to form oxygen gas at 1 atm pressure "At 1500°K and 1 atm carbon monoxide pressure, tantalum oxide, ‘TasO,, isin ‘equilibrium with tantalum carbide, Ta. If the temperature is inroased to 1800°K, the carbide TasC will form, or if at 1500°K the carbon monoxide pressure were increased to several atmospheres, the tantalum earbide would decompose, forming. ‘graphite; a decrease in pressure would result in the formation of the dicarbide TasC. Bample Problem 3-1. Figure 3-8 is « Pourbaix-Bllingham diagram for the ‘Ts-C-O system. Using the data (averaged for the range 208-2000°K) below, caleu- late the equation for the line representing the gas-solid equilibrium between carbon, ‘TasOs, and TaC as shown on the diagram. Also calculate the “10 stm CO(g)”* line shown in the tantalum oxide-graphite field of Fig. 8-8 Compound 30? (ca/mole)—_Sfotng point CR) TiO, = $80,000.4-96.57 2145, te = ama Tce ~s7,000-40.57 373 Tacia)s 31,0004 1.67 3085 Tac <38.0046r — coi) Spero aio = cos) ~84,20 0.37 = Meta ih carbide, 5 Carbon sich carbide, Solution, Expressing the reaction for the gas-solid equilibrium in terms of fone mole of oxygen: Reaction 4G (cal/g-mole) TaOi(s) = #Ta(s) + Os(6) +192,000 — 88.677 (3-2) §Ta(s) + 4C(s) = 1TACIs) -28480 4187 — (6) $Ta0.(s) + IC(s) = $TaC(s) + Os(g) — +168,520- 373 (3-0) «4 5.§, Fourbaie and C, M, Rotive-Boute, Die, Faraday Sit 4y 180 (1048) CW.E, Worrell and J Chipman, Prana. et Soe AINE 200, 168 (1964)32 nit Processes of Betractive Metallurgy ‘The equilibrium constant for reaction (3-c) can be expressed as Kem Pos a) since the solids are at unit activity. ‘Thea the line representing the equilibrium between TasO,, TaC, and C is RP In Po, = AG = 163,520 — 97.8 T eal (Be) Considering a earbon monoxide potential fixed at 10~tatm in the TaOs-C field the equilibrium between earbon, oxygen, and carbon monoxide is 200(«) = 2C(s) + Onte? op “The equilbriurs constant for Ba. (4) is Ky = Po,(10)*. (3b) TariePy = san +a0T + G)QMOGID TG RP In Po, = 53,520 + 78.67. (34) Carbon-Oxygen Equilibria—The Boudouard Reaction ‘The Boudouard resetion, 200(@) = {is composed of the reactions for the oxidation of carbon monoxide D(s) + COn(g), (7) bon to eatbon dioxide and (6) + Ox(e) = COx(B), Gs) C(s) + HOr(g) = COL). 3-9) ‘The corresponding standard free energies of formation for carbon monovide and cearbon dioxide can be represented in the temperature range 1500-2000"K by the relationships, G9 = ~94,755 + 0.027, (240) 6" = —28;200 — 20.18 7 @u) ‘The corresponding free eneray change in the same temperature range for the Boudouard reaction Eq, (87) AGH = 38,55 + 40347 (oa) “The Bowdoward reaction forms the bass fr earbotherme reduction of metals end is extremely important in smelting prootses involving carbon asa redcing gent, to the tos or lead blast furnace proves or the smelting of tin or sine. Prom Fig Purometallurgy II: Oridation-Reduction Reactions 33 3-1, it can be seen that at 1 atm the standard free energy for the oxidation of earbon. to form carbon monoxide and the standard free energy of reaction forthe formation of carbon dioxide are the same ata temperature of approximately 729°C. Below this temperature, carbon monoxide is a mare active redueing agent, wheress above it, solid graphite is the more active reducing agent. The oxidation of earbon will produee a mixture of earbon monoxide and earbon dioxide, but at low temperatures carbon dioxide willbe the predominent component of the gas phase in equilibrium with solid earbon, whereas st higher temperatures earbon monoxide is the pre- dominant gaseous component. Example Problem 3-2. The standard free energies of formation for CO and COs are equal at 710°C. In a system consisting of only carbon and oxygen with excess solid earbon present, what would the gas phase composition be at 1 atm total pressure? At 10~tatm? Solution. Since the A for the reactions, C+ 01= CO, (Ge) 20+ 01 = 200, @) is equal x¢ 710°C, their difference is zero, and log K' = 0 for the reaction, 200 = C + 00s (2) ‘Then at 710°C Poor Kai =F 3a) but Peo = 1 = Peoy (se) Substitution of Eq. (3+) into (8-4) and rearranging, (Poo)? ~ 8Peo +1 = 0; — Poog = 0.882 atm oh Then Xoo, = 0.282, Xeo = 0.618, At 10~atm, a similar ealeulation yields Xco, = 0.0001, The reduction in pressure, following LeChatelier’s Principle, drives Eq. (2) to the lett. ‘Thermodynamic Stability of Sulfides ‘The standard free energies of formation of common metallic sulfides are pre sented on an Ellingham diagram (Fig. 34). The position of the curve for the reaction, 20: +S = 280, Gas) shows that oxygen will displace sulfur from the sulfides of all of the metals except the alkaline earths, ie, an oxidizing roast can be employed to convert sulfides to oxides, as discussed in the previous chapter. In contrast, the postion for the curve34 it Processes of Extractive Metalturay for the reaction, 2H +S = 218 aan shows that hydrogen is not suitable for reducing sulfides, and, similarly, neither is carbon, ‘The possibility of desulfurising stools with ealcium is elearly shown by the position of the line for the reaction, 20a + & = 2Ca8. (318) essen mess serge T Fig. $4, Free Beeay of Formation of Sulfdes Soure: -H. J. % Bingham, J Soe. Chem. Zn, 194, Yo. 68, p. 128, Solty of Chem Ia dusty. Pyromstalurgy IT: Oridation-Reduetion Reactions 35 ‘The ability of manganese to form manganese sulfide in steels during hot rolling is suggested by the position ofthe line for the formation of manganese sulfide relative ‘tg iron sulfide, oF the sulfides of other elements commonly present in steal. Reducibility of Chlorides ‘The Ellingham diagram giving the standard free enorgy of formation of chlotides versus temperature is presented in Fig. 3-5. The pesition of the eurve for the formation of earbon tetrachloride clearly shows that carbon is not a suitable reducing agent for ehlorides, ‘The position ofthe eurve forthe formation of hydrogen chloride indicates that hydrogen is a potential reducing agent for several of the metallic chlorides. Ifthe curve for the standard free energy of formation for a metallie chloride lies above that for the Zormation of hydrogen chloride at a given temperature, the metallic chloride will be redueed to the metal by hydrogen, provided the substances are in their standard states. Conversely, a metal whose chloride lies below the hydrogen chloride curve at a given temperature would, under standard conditions, be ean- verted to the chloride by treatment with HCI gas. The hydrogen chloride curve decreases slightly With increasing temperature, whereas the curves for most of the other eblorides inerease with temperature, thus providing a mare favorable condition for hydrogen reduction st higher temperatures. The hydrogen reduction of ehto- rium chloride is illustrared in the following example problem. Ezample Problem 3-3. The reduction of chromium chloride by hydrogen gas has bbeen proposed as a method for producing pure chromium. Caleulate the purity of hydrogen gas that must be maintained in a reaction chamber at 800°C to carry out the reduetion, CrCh(s) + Ha(g) ~ Cr(s) + 2HCI(g) Solution. Equation (3-8) can be expressed as the difference tetween the reactions, Hi(g) + Ch(g) = 2HCKe), (3) Crls) + Chie) = CrCh(s) (se) the standard free energy change for Eq. (3-8) is AG", = AG, ~ aG% = —48,500 — (63,300) = +14,800eal, (3-4) ‘Thus it can be seen that the reaction is not spontaneous at standard conditions ‘At equilibrium at 800°C, with the solid phases at unit activity From Fig wotac Pa ao, = ~erin [Fasttes] « er in[FH2"| — 1400, @) log (F| =3.017. an Assuming total pressure of 1 atm in the system, Paci + Pay = 1 es)38 Unit Processes of Extractive Metallurgy Teweearung°c [sen come = “MWD 40 TOM MVD Be Sano WON Wwscarmcy V7 krcrcr—-f eer —| Pyrometalturgy I: Onidation-Reduetion Reactions enn 2 J ‘acme g bonrens = i 1— g > | ' 2 : 5 f 2 Pes J ' ve | lu / > oe mescpanet won forgo |? . Fig. 55, Standard Free Energi of Formation fr Metal Chloride aa Funetion of Temperature '3G* between +8,000 snd ~ 160,00 ea Source: HH. Kelog, Trane. AZM, 1059, Vl. 188, p64 3738 Unit Processes of Eatractive Metallurgy Tren Pot = 0.081 atm, Pag = 0.969 atm In order to cause the resetion to occur as written, the concentration of HCI must ‘be maintained below 8:1 vol% (at 1 atm), eg., by removing HCI and adding dry hydrogen to the system. Magnesium chloride is the most stable chloride shown in Fig. 3-5, with the ‘exception of the chlorides of sodium and calcium. The high stability of magnesium chloride forms the basis of the Kroll process for the production of titanium sponge by magnesium reduction of titanium tetrachloride The chlorination of metallie odes ean be accomplished for several metals by heating the oxide in chlorine gas, to allow a reaction of the general form, MO + Ch = MCL + 40s, to oceur. A comparison of the standard free energies of formation of the oxides and chlorides show that this reaction ean readily be earried out at 1000°C for lead, copper, manganese, nickel, ne, tin, and iron. ‘Metals with more stable oxides, such ss magnesium, chromium, titanium, ‘aluminum, and silicon, ean be ehlorinated directly in the preseace of reducing ‘gent such as carbon, catton monoxide, or sulfur. For example MO + Ck +C = MCh + Co, (3.17) Anhydrous magnesium chloride has been produced commercially from MgO using coke and chlorine gas, Titanium tetrachloride can be produced similarly by the chlorination of ilmenite, the most common titanium mineral (nominal composition, FeTi03). Stability of Carbides and Nitrides ‘The standard free energies of formation for severa) metallic carbides and nitrides also are presented in Table A-IT. A eompurizon made between standard free energies of formation of carbides or nitrides in temperature ranges typieal of pyrometallurgical operations will show that titanium and zireonium earbides and nitrides are highly stable, This precludes the possibility of earbothermie reduction of sirconium or titanium oxides except at extremely high temperatures. On the other hand, ion nitride is one of the least stable metallic nitrides, wheress nitrides of chromium, vanadium, and sluminum are much more stable, and as euch are ‘often found as inckusions in steel 3:2 Oxidation-Reduction Reactions Involving Liquid Metallic ‘olutions ‘The foregoing discussion has considered standard free energy changes in which the reactants and produets were present in the most commonly defined state, ie. as pure materials. In practical metallurgical operating situations, reactions ate often | Pyrometllurpy II: Oxidation Reduction Reactions 39 carried out in the pretence of a liquid metallie phase that may have an appreciable Solubility for many of the resetanta and products present. It is necessary under these circumstances to consider the resulting change in the activities of the various components. In some circumstances an advantage in thermodynamic caleulation is realized by changing the standard state. ‘Thermodynamies of Metallie Solutions ‘The chemical activity, a, (the tendency of # component of t phase to react), is dependent upor the concentration of the component in that phase, as well as temperature (see Eq, 3-22). In a solution, the chemical activity of a component is related in some fashion to the amount of the component present. As an example, if Tiquid metal A and liquid metel B are mixed in equal molar proportion, component ‘A might have about one-half the chemical setivity of pure liquid A. If the solution vere more dilute in A, its activity would be less, A component whose activity is divecly proportional to its concentration expressed as mole fraction is said to be ideal and te obey Raoul’s aw: moles A _ na - Moxy ats) = talmoles =n ~~ me Atma = min Eq, (3-18), a = 1. Thus, the pure phase is the reference concen- tration or the slandard sate, The reference concentration could also have been chosen at some other point, For example, « 1 mol % solution could be used as the standard State and the activities indexed from that point. Then, in an ideal solution, the ‘component activities are equal to molar peteentages, .e.,8 1 mol 9% solution would hhave an activity equal to 1, whereas & pure solution of a component would have ait activity (index) of 100, ‘Other standard states often are used as well. For a gas, the standard state is taken usually as I atm pressure of that particular gas component. An ideal gas with ‘partial pressure of 1 torr (1 mm of mercury) would have an activity of 1/760. If however, 1 tort had been chosen as the standard state, the activity would be equal to Tif the gus component wore at a pressure of 1 torr and equal to 760 8t 1 ‘Standard atm. In metallic solutions, a standard state often is chosen such thot the ‘tivity at infinite dilution is equal to the concentration in weight percent. This ‘standard state, referred to as the hypothetical 1 w1% solution, often is ennvenient since compositions in industrial practice generally are expressed in weight pereent. Free Energy and Activity, The free energy of & component, i, is related to the ‘chemical activity of the component by the relationship 6, G2 = RT In (a,) = 4.575 T loge (a), (319) where Gis the free energy of component i within the phase and G of the component in its standard state in which a? = 1 (Nonideal Solutions. Most real solutions ate not ideal. In order that a solution be ideal, the etamie species of the component must interact with those ofthe other components in the same manmer that they do with their own, "The activity of silicon in molten iron is shown in Fig. 3-6, Silicon does not is the free energy