Stoichiometry and thermodynamics of metallurgical processes Y. K. RAO Professor of Metallurgical Engineer Universty of Washington, Seale, Washington \ MBRIDGE UNIVERSITY PRESS Ca bridge Loita New York New Rochelle Melbo. ve Sydneypublished by the Press Syndicate f the University of Cambridge ‘The Pitt Building, Trumpington Stet, Cambridge CB2 RP 432 East STth Stret, New York, NY 10022, USA 10 Starnford Road, Oakleigh, Melbourne 3166 Austalia (© Cambridge University Press 1985 First published 1985, Printed inthe United States of America Library of Congress Cataloging in Publication Data Rao, YK Stoichiometry nd thermodynamics of metallurgical processes Includes bibliographical references and index 1 Metatlrgy. 2. Chemistry, Physical and theoretical. 1. Tite TNG.RIG 1985 6699843004 ISBN 0 521 25856 1CONTENTS Preface Chapter |. Introduction ra 12 13 14 1S Definitions Measurement of quantities: units and dimensions Gram-mole, kilogram-mole, pound-mole, and gram-atom Composition Behavior of gases and vapors 1.6 > Gaseous mixtures Worked examples Problems References smetry: material balances in metallurgical processes Stoichiometry Law of conservation of mass Method of calculation Blast-furnace charge-balance calculations Material balances in copper smelting and converting Continuous copper-smelting processes Unsteady-state operations: the basic oxygen process Worked examples Problems References Chapter 3. First law of thermodynamics 31 32 33 34 35 36 37 38 39 Work Heat First law of thermodynamics Heat and work changes in reversible processes Heat capacity Calculation of enthalpy chatiges Reversible adiabatic process Energy balances in simple systems Energy balances in complex systems Worked examples Problems References z page xiiiviii Chapter 4. Fuels and combustion 4.1 Energy resources 4.2 Coal resources 4.3. Classification of coal 4.4 Metallurgical coke 4.5. Gaseous fuels 4.6 Gasification of solid fuels 4.7 Liquid fuels 4.8 Combustion Worked examples Problems References Chapter 5. Energy balances 5.1 Application of energy balances 52. TFT ina blast furnace 5.3. Roasting of copper sulfide concentrates 5.4 Fluid-bed roasting of zine concentrates ‘ 5.5. Heat balance in an iron blast furnace 5.6 Energy consumption in metallurgical processes Worked examples Problems References Chapter 6. Second law of thermodynamics 6.1 Introduction 6.2 Statement of the second law 63 _ Efficiency of a heat engine 6.4 The Carnot cycle 6.5. Some consequences of the second law 6.6 The concept of entropy 6.7 Entropy changes in typical reversible processes 6.8 Entropy changes in some irreversible processes 6.9 Entropy change of the universe in a reversible process 6.10 Entropy change of the universe in an irreversible process 6.11 The Clsusius inequality 6.12 Combined statement of first and second laws 6.13 Some useful thermodynamic relationships 6.14 Difference between heat capacities Cp and Cy 6.15 Entropy of an ideal gas 6.16 Absolute value of the entropy of a substance 6.17 Entropy change for irreversible chemical reactions Problems References Chapter 7° Auxiliary functions 7.1 The Helmholtz free energy and the Gibbs free energy 7.2.” Free-energy equations in differential form Contents 88 88 88 96 102 im 13 1B 133, 447 17 182 15, 185 185 185 186 186 187 188 205 207 208 208 208 209 209 213, 216 218 219 22a 222 226 227 228 232 233 236 238 239 242 —$——Stoichiometry and thermodynamics of metallurgical processes Y. K. RAO Profesor of Metallurgical Engineering Univernty of Washington, Sead, Washington \ MBRIDGE UNIVERSITY PRESS Ca bridge Loita New York New Rochelle Melbo. ae SydneyPublished by the Press Syndicate of the University of Cambridge ‘The Pit Building, Trompington Street, Cambridge CB2 1RP 432 East 57th Street, New York, NY 10022, USA 10 Stamford Road, Oakleigh, Melbourne 3166 Australia ‘© Cambridge University Press 1985 First published 1985 Printed inthe United States of America Library of Congress Cataloging in Publication Data Rao, ¥.K, Stoichiometry nd thermodynamics of metallurgical processes Includes bibliographical references and index. 1 Metallurgy. 2. Chemistry, Physical and theoretical. I. Tite, TNGT.RSG 1985 669!.9 ISBN 0 521 25856 1 320To PADMA AND RAM, VIJAY, AND RUPAContents 7.3. Free-energy changes for an ideal gas 7.4 Thermodynamic potentials 7.5 The Maxwell relations 7.6 Criteria of equilibrium 7.7 Criteria of spontaneity (or irreversibility) 7.8 The Gidbs-Helmholtz equation 7.9 The Gibbs free-energy changes in typical reversible processes 7.10 The Gibbs free-energy changes in typical irreversible processes 7.11 The third law of thermodynamics 7.12. Evaluation of absolute entropy Problems References Chapter 8. Theory of solutions | 8.1 The Gibbs free energy of an ideal gas 8.2 Mixtures of ideal gases 83. The fugacity function 8.4 Evaluation of the fugacity of a real gas 8.5 “Mixtures of real gases 8.6 Fugacities of condensed substances 8.7. Definition of activity 8.8 Partial molar quantities 8.9. The partial molar Gibbs free energy 8.10 Other partial molar quantities 8.11 Partial molar quantities of ideal-gas mixtures 8.12 Integral molar quantities 8.13 Method of determining partial molar quantities from integral molar quantities 8.14 Integration of the Gibbs-Duhem equation 8.15 Relative partial molar quan 8.16 Relative integral molar quantities 8.17. Temperature dependence of activity 8.18 Raoult’s law and ideal solutions 8.19 Dilute solutions and Henry's law 8.20 Determination of activity by integration of the Gibbs- Duhem equation 8.21 Determination of Hi! and H™ from data on Hi 8.22 Deviations from the ideal: excess thermodynamic quantities 8.23. Regular solutions Problems References Chapter 9. The Gibbs free-energy change and the equilibrium constant 9.1 Introduction 9.2 Equilibrium constant 9.3. Equilibrium constant for an all-gas reaction: ideal gases 9.4 Equilibrium constant for an all-gas reaction: real gases 9.5 Le Chatelier’s principle ix 245 246 248 248 250 252 234 255 256 262 263 267 268 am 2m 275 277 314 319 321 321 322 324 330 332x Coritents | 342 9.6 Heterogeneous reactions 338 j 9.7 Temperature dependence of AG” and K 9.8 Frec-energy equation for formation of MgO 345 | 9.9. Sources of thermodynamic data 360 | 9.10 Simplified three-term and two-term free-energy equations 363 i 9.11 Free energy of formation for inorganic substances 366 ! 9.12 Free-energy charts and Ellingham diagrams a if 9.13 Experimental methods for determining AG} for reactions at high temperatures 388 9.14 Systematic thermodynamic treatment of experimental data on K : and AG? 390 9.15 Electrochemical systems 401 9.16 High-temperature galvanic cells 417 9.17 Electrolysis 428 9.18 Dilute solutions of gases in condensed phases 434 9.19 Alternative standard states 438 9.20 Activity data from experimental measurements 444 9.21 Interaction coefficients in multicomponent systems‘ 467 Problems 478 References 503 Chapter 10. Phase equilibria 508 10.1 Definition of terms 508 10.2 Phase equilibria and equality of chemical potentials in all phases. 509 10.3 Nonequilibrium systems and phase stability 510 4 10.4 The phase rule for nonreactive components si 10.5 The phase rule for reactive components 516 10.6 Phase changes in single-component systems 520 10.7 Effects of pressure on the Gibbs free energy and activity of a pure ‘ condensed phase 528 | 10.8 The Gibbs free-energy change accompanying vaporization of : a condensed phase 530 B 10.9 Temperature dependence of AG” for phase transformations 534 ; 10.10 Experimental data on vapor pressures: systematic treatment 542 10.11 Phase equilibria and chemical equilibria 352 10.12. P~T—x equilibria involving condensed phases 562 t 10.13 Free-energy—composition curves and equilibrium phase diagrams 568, : 10.14 Examples of construction of binary phase diagrams 37 10.15 Thermodynamic data from phase diagrams 582 10.16 The iron—carbon system 589 10.17 Systems with intermediate compounds of variable composition 601 10.18 Metal—oxygen systems with intermediate compounds of variable composition 604 10.19 The iron~oxygen system 606 | 10.20 Thermodynamic quantities for homogeneous metal~gas solutions 616 Ho 10.21 The uranium—carbon system 619 10.22 Further comments on phase equilibria in oxide systems 620 10.23 Metal-sulfur—oxygen systems: stability diagrams 26——$<$____--— - Contents 10.24 30.25 10.26 10.27 10.28 The lead—sulfur-oxygen system The copper~sulfur-oxygen system The copperhydrogen-chlorine system Isothermal-stability diagram for the Cu-H—C1-O system Equilibrium and stoichiometric calculations in chloride systems Problems References Chapter 11. Equilibria in complex systems ud 41.2 3 us WS 1.6 17 118 19 11.10 mw Heterogeneous reaction systems Conventional methods in equilibrium calculations Stoichiometry of chemical reactions Analysis of typical metallurgical systems Complex equilibria: modern methods Computation of complex equilibria on a high-speed digital computer by the iterative method Complex equilibria in crystal growth systems: iterative method Vaporization equilibria Convergence aids Free-energy-minimization method Adiabatic systems Problems Appendix References Chapter 12. Theory of solutions Il 121 12.2 123 24 25 126 12.7 128 Composition dependence of activities in binary solutions Statistical thermodynamics of solutions Mixtures of fused salts Regular-solution model for fused-salt mixtures Application of the Gibbs-Duhem equation to complex systems Chemical-species models applied to associated solutions ‘Thermodynamics and constitution of slag systems Flood-Grjotheim treatment of ionic melts Problems Appendix References Appendix A: Units and conversion tables ‘Appendix B: Program FUELGAS Appendix C: Thermochemical data Appendix D: Vapor-pressure equations Appendix E: Matrices and vectors Answers to problems Nomenclature Index 692 m3 738 748 755 51 64 765 7B 74 790 818 821 821 827 833 834 835 847 855 860 863, 368 870 873 879 895, 896 909 937 948PREFACE This text book is written primarily for students in metallurgy and in allied fields such as materials science, physical chemistry, chemical engineering, and fuel technology. The intent is to introduce the student early on to the fundamentals of the physical chemistry and the thermodynamics of metallurgical processes and then gradually expand the treatment into progressively more advanced areas. ‘At one time, instruction in extractive (process or chemical) metallurgy con- sisted solely of studying process descriptions and operational details. At a few places this approach may still be in vogue, but for the most part; a much sounder approach has taken root, with emphasis on quantitative analysis of metallurgical processes. At the minimum, this latter approach should provide instruction in topics such as stoichiometric principles, material balances of metallurgical reactors, the laws of thermodynamics, energy consumption in metallurgical pro- cesses, chemical equilibrium, phase equilibrium, heterogeneous systems, and solution theory. Such a wide range of topics obviously cannot be covered in a single course, unless one compromises the quality of instruction severely. This text provides a comprehensive treatment of these and a variety of other topics, The material presented here has formed the basis of three sequential courses offered by the author for some years at the University of Washington and at Columbia University. The suggested course organization is as follows: Stoichiometry: material and energy balances: Chapters 1 through $__ Introduction to thermodynamics: Chapters 3, 6, 7, 8, 9 (Sections 9.1-9.7, 9.9, 9.12, and 9.15), and 10 (Sections 10.1, 10.2, 10.4, 10.6, 10.7, and 10.23) Advanced thermodynamics: Chapters 9 (Sections 9.8-9.11, 9.13, 9.14, and 9.16-9.21), 10 (Sections 10.3, 10.5, 10.8~10.22, and 10.24—10.28), 11, and 12 ‘The first two courses are to be offered at the undergraduate (junior-senior) level, and the final course, which draws heavily from the last three chapters, best fits the graduate curriculum. Each chapter contains a substantial number of illustrative examples, the pur- poses of which are to demonstrate tiie application of the theoretical principles and to provide further elaboration of the text, In Chapters 1~5, the examples have been separated from the main body of the text and grouped together at the end of each chapter. This is because most of these examples are unusually long and ‘would tend to interrupt the flow of the theoretical discussion. In the remaining chapters, the examples blend well with the textual material xiiI xiv Preface | In addition, several problems are included at the end of each chapter; solving these should deepen the student's understanding of the subject. The examples and : problems can be divided into two groups: Group I: Simple examples and problems that relate to idealized conditions and processes. Often these involve only straightforward application of the formu- las given in the text. Group II: Project-type examples and problems that require in-depth analysis and | ‘may draw on material from several chapters. | ‘The examples and problems in group Il are indicated by asterisks. These may be | attempted after the student has developed some mastery over the subject by careful and repeated consideration of the examples and the group I problems, ‘Apart from being the student's companion, itis hoped that this book may also serve as a reference text, particularly in light of the fact that a broad range of subjects is covered. Chapter 4 gives an overview of fuels, gasification, and combustion, topics that are of considerable interest to metallurgists, chemical engineers, and fuel technologists. Chapter 5 develops the energy balance for an iron blast furnace in greater detail than is available elsewhere. The second- and third-law analyses of equilibrium measurements presented in Chapter 9 should be 1 of particular interest to researchers in high-temperature chemistry. The discus- sion of the Gibbs phase rule in Chapter 10 is more detailed than that in most i elementary texts. Also presented in Chapter 10 is an in-depth analysis of the iron—oxygen and iron~carbon systems, as well as a cogent description of the stability diagrams for ternary and quaternary systems. Chapter 11 is somewhat ‘unusual in that it s one of the few attempts ever made to combine the classical thermodynamic approach with the rapid computational capability of a modern digital computer. The material in this chapter is suitable for metallurgists, materi- als scientists, chemists, chemical engineers, fuel technologists, and semiconductor . specialists. The several computer programs included here have all been run ; successfully on the CDC Cyber 170-750 unit at the University of Washington Academic Computer Center. ‘A two-tier approach is followed in developing the theory of solutions. The more elementary topics are introduced early in Chapter 8, thus paving the way for further discussions of appropriate topics in Chapters 9, 10, and 11. The more advanced subjects, such as ternary Gibbs-Duhem integration, statistical thermo- dynamics of molten alloys, fused salt mixtures, associated solutions, and slag equilibria, are dealt with in some detail in Chapter 12, The appendixes provide a selection of thermodynamic data and include a compilation of free-energy equa- tions for a large number of inorganic compounds. In preparing this text, I have drawn inspiration from many sources, the most ' notable being the writings of L. S. Darken, C. Wagner, F. D. Richardson, R. Schuhmann, Jr., O. Kubaschewski, H. H. Kellogg, J. Chipman, J. F. Elliott, C. B. Alcock, and E. T. Turkdogan. These men, through their research and| | r | { i Preface xv publications, have profoundly altered and enriched the landscape of metallurgical thermodynamics. Many influences have helped to mold my views and understanding of thermo- dynamics. I am pleased to acknowledge my indebtedness to my former teachers, especially Professors V. K, Agarwal and G. R. Belton, and also my former colleagues at Columbia University, most notably Professor H. H. Kellogg for introducing me to the applications of digital computer methods in thermo- dynamics. Lowe a formidable debt to my senior colleagues at the University of Washing- ton. Many of my former and current graduate students rendered valuable assis- tance by reading parts of the manuscript and by checking answers to the problems: H. G. Lee and H. G. Han have uncomplainingly assisted me in verifying the accuracy of the computer programs appearing in this text and J. H. Haberman was also helpful. I wish to thank them, I am also grateful to several groups of students who took the courses Met.E. 322, Met.E. 421, Met.E.464, and Met.E.523 at the University of Washington and solved homework problems drawn from this text, thus providing an independent check of the answers. A large measure of thanks goes to Mrs, Marianne Kissack for her accurate and painstaking typing of the manuscript. Special gratitude is expressed to David A. Tranah, Editor, Cambridge Univer- sity Press, for his careful editing and thoughtful, constructive criticism of the manuscript. Finally, special mention should be made of my family. But for the enormous patience and unswerving support of my wife and the constant encouragement of my children, this book would never have been finished. I am fortunate to have them. Y.K. RAO Seattle, Washington December 1984INTRODUCTION LI Definitions A.system a portion of the universe that we have chosen forstudy. The remainder of the universe is called the surroundings. A closed system is enclosed by an impermeable boundary or wall that does not permit the transfer of matter but allows transfer of energy. The mass of a closed system remains constant. ‘An open system is bounded by permeable walls that allow the transfer of both ‘matter and energy across the walls. ‘An isolated ‘system is a system enclosed by impermeable walls that permit neither exchange of energy nor transfer of matter. Such walls are termed adiabatic walls ‘A homogeneous system is made up of a single phase; a heterogeneous system consists of two or more phases ‘A reactor is the physical apparatus in which chemical reactions take place. The reaction mixture isthe entire material within the reactor. It consists of reactant and product species, and in some instances it may include catalytic substances or inert species. ‘The state of a system is defined by specifying state variables or state properties, namely, temperature, 7, pressure, P, volume, V, and composition. When dealing with heterogeneous systems it is necessary to specify additional parameters such as the particle size distribution or the surface area of the particulate matter. 1.2 Measurement of quantities: units and dimensions Several different kinds of units have been in use for measuring mass, length, volume, pressure, and temperature in a system. Some of the most commonly used sets of units are listed in Table 11. The factors used for converting from one set of units to another are provided in Table 1~2 and in Appendix A. The units of mass, length, and volume require no further discussion. Pressure measurement Pressure is defined as force per unit area. It may be expressed in pascals (Pa), millimeters of mercury (mm Hg = Torr), feet of water, pounds of force per square inch (Ibyin.”), or standard atmospheres. The pressure measured may be absolute or relative. Measuremient against a perfect vacuum yields absolute pressure. Gauge pressure, on the other hand, is a relative quantity obtained when the measurement has been made against atmospheric pressure. Thus, 12 1 Introduction Table 1-1. Most common units Engineering units. Quantity cos FPS English American Length m cm ft ff Time ‘ see sec see sec see Mass ke ke ® ib slug by Moles mol kgmole —gmole —_Jbsmole_—_Ib-mole_Ibmole Temperature K *K(or K) °C °F or Volume liter mi(orcam) mi(orem!) f° ee Force newton (N) N dynepoundal Ib wt. by Pressure pascal (Pa) Nim dynelem? —poundalt? theft? Tot? Energy joule) J erg fepoundal_Blu__ Bru, bp-hr Multiple-unit prefixes: nano (n) = 10? cent (@) = 107 micro (4) = 107 ‘ ‘milli (m) = 10°? absolute pressure = gauge pressure + atmospheric pressure (a-1) Atmospheric pressure is the pressure of air that is around us; this pressure, although it changes from one day to the next, does not deviate greatly from 760 mm Hg (or Torr). The unit standard atmosphere or simply atmosphere, unlike atmospheric pressure, is a fixed quantity; itis defined as the pressure exerted, under standard gravitational conditions, by a column of mercury 760 mm high at a temperature of 0°C. This may be expressed in various units, as follows: 1,000 atmosphere (atm) = 101,325 pascals (Pa) 760.000 millimeters of mercury (mm Hg, or Torr) 29.921 inches of mercury (in. Hg) 33.910 feet of water (ft H,0) 14.696 pounds per square inch (Ibgin.?) ‘The most commonly used engineering units for pressure are pounds per square inch (psi) and inches of mercury (in. Hg). Absolute pressure is abbreviated as ‘psia” (pounds per square inch absolute). Gauge pressure is abbreviated as “psig” (pounds per square inch gauge). ‘Temperature measurement ‘The temperature of a system can be measured either in degrees centigrade (also known as Celsius) or in degrees Fahrenheit. The most common scientific scale is the centigrade scale, in which 0°Cis the ice point of water and 100°C is the normal boiling point of water. In daily life, and in some engineering applications, the Fahrenheit sale is preferred. In this scale, 32°F represents the ice point and 212°F denotes the normal boiling point of water. The Kelvin (or absolute) and Rankine scales are related to these as follows:1.2. Measurement of quantities 3 Table 1-2. Conversion factors and units Volume Time Mass Force Pressure ‘Temperature Energy Power 3937 in, = 0.032808 ft 1mm = 10-* m 1 micron (1) 1 angstrom (A 1 liter = 1000 em? 1 eubie meter (m') = 35.315 f° 1 gal (U.S.) = 231 in? 1 gal (U.K.) = 277.42 in. = 4.546 liters = 0.004546 m? 1 hr = 60 min = 3600 see 11 kg = 1000 g = 2.2046 pounds mass (Ibq) = 6.8521 x 10°? slugs 1 Ibq = 16 ounces (02) = 0.45359237 kg = 7000 grains (Troy) 1 ton = 2240 fbg = 1016 kg “ I metric ton = 1000 kg = 2204.6 lbp 1 short ton = 2000 Ibg = 907.2 kg I newton (N) = 1 kgrin/sec? = 10° dynes 1 dyne = 1 gremisec! 1 kilogram force (kg) = 9.80665 N 1 pound force (Ib) = 4.448 x 10° dynes = 4.448 N 1 poundal = 13,826 dynes = 0.13826 N 1 pascal (Pa) ='I Nim? = 10 dyneslem? 1 atm = 14.696 Ibgin.* = 760 Torr = 1.01325 x 10° dynesiem? 1 mm Hg = 1 Torr = 0.01934 Ibyin.? = 1.33322 x 10° dynesfem? 1 bar = 10° dynesiem? = 10° Pa = 0.98692 atm 1 Mogi, 708.1 kim? 1 micron (wu) 0-3 mam Hg = 0.133322 Pa T degrees Kelvin = 1 degrees centigrade + 273.15, 1 degrees Fahrenheit = 1.8 degrees centigrade + 32 T degrees Rankine = 1 degrees Fahrenheit + 459.67 1 joule (J) = 1 kgm*isec? = 10? grem*sec? = 107 exes 1 cal (thermochemical) = 4.184 J 1 eal (international steam table) = 4.1868 J 1 Btu = 778 ft-lby = 1084.35 J = 252 cal 1 keal (thermochemical) = 1000 cal = 3.968 Bru 1 electron volt (eV) = 1.6022 x 10° 3 J watt (W) = 1 kgm*ésec! = 1 Jsec 1 horsepower (hp) = 550 ft'lbysec = 746 W 1 kilowatt (kW) = 1000 W = 3414 Brufhr micrometer (um) = 10°* 0" TK) = (°C) + 273.15(°K) (-2) TER) = 1(F) + 459.670) a-3) 8 (°C) + 32 (4) CRYLS. (-s)4 1 Introduction we ‘nr igure 1-1, Comparison of siterent —LUrUrUt~———Cs,—F_L rrr | Aegree CTP onyeen = trols pone ofongeen). | I ances 6584 bazo—tzer| rer \] ce point 273] fo as24 bse Figure 1-1 shows a comparison of Kelvin, centigrade, Rankine, and Fahrenheit temperatures. The fixed-point temperatures shown in this figure are from the International Practical Temperature Scale of 1968. Many devices are available for measuring the temperatures of systems, includ- ing (1) liquid-in-glass thermometers, (2) constant-volume gas thermometers, (3) resistance thermometers or thermistors, (4) thermocouples (¢.g.,iron-constantan and chrome!-alumel), and (5) optical and radiation pyrometers. Figure 1-2 shows the ranges of temperatures over which these devices can be used.’ 1.3 Gram-mole, kilogram-mole, pound-mole, and gram-atom ‘A gram-mole (g-mole) of a substance is an important quantity in the CGS and SI systems of units and is 6.022 x 10® molecules of the substance: In other words, a gram-moleis the mass of Avogadro's number of molecules. In the MKS system of Units, the more common unit is the kilogram-mole (kg'mole), which is 6.022 10° molecules. The engineering system of units makes use of the pound-mole (lb-mole), which is 453.6 x 6.022 x 10 molecules. A gram-atom (g-atom) consists of 6.022 x 10 atoms of the element under consideration. For mona- tomic molecules the gram-mole and the gram-atom are the same. For convenience, we shall use mole to signify gram-mole. Although a fuller discussion of the properties of gases is deferred to a later section, it is useful to consider here terms such as the molar (or mola!) volume, V, which is the volume occupied by 1 mole of the substance.* The molar volume is defined with respect to either 1 g-mole or 1 Ib-mole at a specified temperature and pressure. Of particular interest are the standard temperature and pressure conditions (abbreviated STP or NTP); 0°C and 1 atm (760 mm Hg at 0°C). At STP, 1 g-mole of an ideal gas ‘occupies 22.415 liters (0.022415 m?), and 1 Ib-mole of an ideal gas occupies 359.06 #8, Abbreviations such as Nm (normal cubic meter) and SCF (standard cubic + For simplicity, we shall often use the symbol V for molar volume, reserving V only when itis necessary 10 avoid confusion 51.3. Molar quantities 5 Fy) x 500] te ns — 221 0 2300 | 2200 $29 20} 2 sop oyptena as sce teidion mets 799° 500} 2800 Sean toa 2400 2300 4500 - 000] 209 2800 Alumina bit 2100 Abmina nets oog—1-2000 ecm aes 000 ; = oo | em nts 1800 op A yoo Worcs” 1600 ideas 1500 Siem 000g) 00 1300 ‘eee 1800 Game 7% 2000] 1100 \ Sher wate 00 Jt ae aes mets es a] IEEE 2000 | |z i Sudiom eoride eats 1500] 200 e/ ie |E/ eg | SP ooo 2] |e |2lz|2 2 \g are 1300 oo = || is fel gle 1000 3| z/e}s suite bois 00 f/ | fEalz _ 2| (2 (elelele Mee bas PEaYy 000 59g) 300 ggg Hielajel ~ Sel e]E/2 x2! 100 z\5 ate tenes —S0222-—g27315- | ype is oa) Syren as 2 . Nols 0 -439.58 -27315 0 “Absolute ae Figure 12. Temperature-measuring devices and their ranges of operation. (Adapted from D.M, Himmelblau, Basic Principles and Caleulations in Chemical Engineering, 3rd ed., Prentice-Hall, Englewood Cliffs, N.J., 1974, with permission.) foot) are sometimes used to designate m* (STP) and fe? (STP), respectively Molar volume has units of em?/g-mole, liters/g-mole, fr'fIb-mole, and so on. ‘Specific volume, V. is defined as the reciprocal of density; thats, itis simply the volume occupied by’ specifie amount of the substance. The units of specific volume may be cm'/g, litersig, or ft°Ab. :6 1 Introduction 1.4 Composition ‘The evolution of a reacting system can be studied by monitoring the changes occurting in the composition of the reaction mixture. The composition can be expressed in terms of mole factions or mass fractions. Ifthe mixture consists of moles of component 1.and nz, ns, .. . moles of components 2, 3, . . . ,then the mmole fraction of the ith component is given by a= nln) a-6 Ifm,, ma, are the masses of components 1,2, . . . , then the mass fraction of the th component is defined by y= mim) a-7) ‘The mole fraction x; of the ith component is related to the mass fraction y,. If My, Ma arethe molecular weights of components 1,2, .. ,itean be shown that a= VIL + Ody) EM) a + (Milyd E AOyl MN a8) 1.5 Behavior of gases and vapors For any substance there exists a unique relationship between its state properties; this relationship is known as the equation of state. In general, we can write S(P,V,T) = 0 a-9) where P, V, and T are state properties of the substance. For a hypothetical substance called the idea! gas (or the perfect gas), this relationship assumes the following form, the ideal-gas law: PV = nT (1-10) where Pis the absolute pressure of the gas, Vis the volume occupied by the gas, T is the temperature of the gas, n is the number of moles of the gas, and R is the ‘universal gas constant. Under most conditions, P-V-T relationships for real gases fare quite complex compared with the ideal-gas law. At Jow densities, which are approached at high temperatures and low pressures, most gases tend to behave like an ideal gas. The behavior of some gases over a range of pressures is shown in Figure 1-3. The value of (PVinRT) approaches unity (ideal-gas behavior) as P— 0. Athigher pressures, the deviation from ideal-gas behavior is appreciable, Value of R, the universal gas constant If an ideal gas occupies volume V; at pressure P; and temperature T), and occupies volume V3 at pressure P> and temperature T>, then P,Vs/T; = PaVo/Tz = constant a=n) ‘The molar volumes V, and V2 are given by Vy =Viln and V2= Vola a-12) On combining equations (1-10), (1-11), and (1-12), we obtain1.5 Behavior of gases and vapors 1 Figure 1-3, Real gases approach jdeal-gas behavior under limiting conditions. (Adapted from D. M. Himmelblau, Basic Principles ‘and Calculations in’ Chemical Engineering, 31d ed., Prentice-Hall, Englewood Cliffs, NJ., 1974, with permission.) PN2/T; = R a-13) ‘The value of R can be calculated as follows: At STP (where Po = 1 atm and Tp = 273.15°K), the molar volume of a gas is Vo = 22,415 cm*/g-mole or 22.415, liters/g-mole. Thus, R = PyNo/To = 22.415/273.1 (0.08206 liter-atm/g-mole*K In CGS units, Po = 1.01325 x 10° dynesiem? Tp = 273.15°K and Vo = 22,415 em*/g-mole Then R = (1.01325 x 10°) (22,415)/273.15 8.3143 X 10” ergsig-mole"K = 1.98717 callg-mole"K In SI units, Po = 1.01325 x 10° pascals To = 213.15°K and Vo = 0.022415 mig-mole ‘Thus, R = (1.01325 x 105)(0.022415)/273.15 = 8.3143 g-mole-"K In MKS units Po = 1.01325 x 10° Nim? To = 273,15°K and Vo = 22.415 m°/kg-mole 82,06 cm -atmig-mole*K Substituting, R = (1.01325 x 10°)(22.415)273.15 = 8314.3 Jikg-mole*Ka 8 1 Introduction In engineering units, 4.696 Ibvin.? = 14,696 (144) = 2116.2 Ibi? 191.67°R and Vo = 359,06 ft'b-mole Thus, R = 2116.2 (359.06)491.67 1545.45 felbilo-mole-’R = 1.987 Biuilb-mole"R Imperfect gases (real gases) ‘The behavior of imperfect gases can be described by the virial equation of state PV = n(RT + BP + CP +--+) a1) PY=RT+ BP+CP+- a (1-15) where B,C, . . . are known as the second, third, . . . virial coefficients. For a given substance these coefficients depend only on T, the temperature. ‘At moderate densities the behavior of real gases can be fairly accurately represented by these series truncated at the second term. That is, PV = nRT + nBP a-16) or PV = RT+ BP a-17) At low pressures, the second term, BP, becomes insignificant, and equation (1-11) reduces to the ideal-gas law. Another powerful P-V-T relationship that describes the behavior of real gases rather well is the van der Waals equation of state: (P+ a/V°YV — b) = RT (-18) where a and b are constants for any given substance. The values of these con- stants, however, differ from one substance to another, as shown in Table 1-3. At sufficiently low densities, where the specific volume will be very large, the terms a/V? and b become negligibly small compared with P and V, respectively Under these conditions, the van der Waals equation of state reduces to the ideal-gas equation. 1.6 Gaseous mixtures Dalton’s law and Amagat’s law are important physical laws that apply to gaseous mixtures. To understand these laws, we may consider a gaseous mixture made up of three nonreacting components (1, 2, and 3). The molecules of each component gas are free to move randomly throughout the volume of the container. Thus, ‘each gas can be regarded as occupying the entire volume, Moreover, each compo-1.6 Gaseous mixtures 9 Table 1-3. Van der Waals constants a and b > Substance [em (kg-mole}*] (mitkg-mole) He 3.440) 0.0234 Hy 24,800 0.0266 0.0318 0.0429 0.0319 0.0575 N 0.0391 co 0.0399 cH, 0.0427 Hg 0.0055 Note: P is in units of Nim®, V in mikg-mole, T in °K, and R= $314.3 Jkg-mole:"K. To convert a 10 CGS units, atmem*? (g-mole)?, multiply the table value by 2 factor of 9.869; to convert 6 to em'/g-mole, multiply the table value by 1000. In CGS units, P is in atm, V is in em/g:mole, T is in °K, and R = 82.06 cm-atmig-mole-*K. nent is expected to obey the ideal-gas law at ordinary pressures. Assuming that there is 1 mole of each of the three gases in the mixture, we can write PIV=RT, PV = RT, and P3V = RT (19) Dalton's law states that the total pressure, P, of the mixture is equal to the sum of the partial pressures. In other words, P=Py+ Prt Ps 1-20)" ‘The application of Dalton’s law is illustrated in Figure 1-4. Amagat’s law relates the total volume of the mixture to the hypothetical partial volumes occupied by the components. Figure 1~5 clarifies the application of Amagat’s law. According to this law, the total volume occupied by a gaseous mixture at a given pressure and temperature is equal to the sum of the pure component volumes at the same pressure and temperature. For the pure compo- nents 1, 2, and3 that appear in Figure 1-5, assuming, = nz = ns = 1, we have PV; = RT, PV; = RT, and PV; = RT 21) For the entire mixture, PV=(+14+0)RT : PV = 3RT (1-22) “Altematively, we can write P, inthe cP, were x, is the mole fraction ofthe ith compor10 1 Introduction Component 2 Component 3 Figure 1-4, Dalton’s law of, partial pressures. (Adapted from M. L. Smith and K. W. Stinson, Fuels and Combustion, McGraw-Hill, New York, 1952. with permission ) Mintuce Component) Component 2_-—_Component 3 : mo tne nT Figure 1~5. Amagat's law of partial volumes. (Adapted from M. L, Smith and. KW. Stinson, Fuels and Combustion, McGraw-Hill, New York, 1952, with permission.) Appropriate algebraic manipulation of equation (1~21) yields POV, + Va + Vs) = 3RT 23) From eguations (1~22) and (1-23) it follows that VEV+VetVs (1-24) Both of these laws are very useful in physicochemical calculations involving gases and vapors. ‘The average molecular weight of a gas mixture can be found by treating such a mixture asif it were a single gas. Example 1~6 a the end of this chapter serves to illustrate the procedure. Dissociating gases At clevated temperatures, some gases tend to dissociate, and the resulting gas mixture does not obey the ideal-gas law, although each component may behave as an ideal gas. The tendency of arsenic and antimony to dissociate into smaller molecules is well known: ‘Sba(g) = 2Sb(g) (1-25) Thus, antimony vapor is not a pure diatomic gas, but a mixture composed of two gases: Sbz and Sb. The dissociation produces two molecules from one, and the pressure or volume of the gas mixture will be in excess of what would exist had no dissociation taken place. Thus, when 1 g-mole of liquid antimony is vaporized, itis not possible to predict the exact volume occupied by the gas on the basis of ‘equation (I~ 10) alone. (Example 1-7 is instructive.)1.6 Gaseous mixtures ul Figure 16, Vaporization of pure water ino aie at constant presure find temperature. (Adapted. trom D.M. Himmelblav, Baie Principles tnd Colelaions in Chemical Engineering. 3rd ed, Prentice-Hall. Englewood Cit. NJ. 1974 with permission.) Air-water vapor mixtures In metallurgical engineering there are many processes in which air is used as a reactant. When dry air is placed in contact with water, it will gain vapor from the water phase. If the contact is prolonged, the air will become saturated with water vapor. As an example, let us consider dry air at 40°C enclosed in a container in which there is some water. The container is fitted with a smoothly moving piston. ‘The arrangement is shown schematically in Figure 1~6. The total pressure on the piston is constant at all times at 760 mm Hg. Under these conditions, water wil vaporize, and the vapor will join the dry air, giving rise to humidified air. The vaporization will continue until the pressure of the water vapor in the air reaches 55.3 mm Hg, which value is the equilibrium (or saturation) vapor pressure of water at 40°C. Table 1-4 provides data on the equilibrium vapor pressure of water at several different temperatures. ‘Assuming that both air and water vapor behave like an ideal gas, we can calculate the partial pressure of air at saturation using Dalton’s law for partial pressures: Pair + Pr Pai 760 mm Hg 760 ~ 55.3 = 704.7 mm Hg If Vis the volume of the air-vapor system at complete saturation, then PaoV = myoRT and Py,V = ryieRT where my,o and na are the numbers of moles of water vapor and air, respective- ly. Alternatively, we can write Puyo = tH,0P = 760%1,0 (1-26) and Pig = xaipP = 760%, a-27) where xy,0 and Xi are the mole fractions of water vapor and air, respectively. If the time of contact between air and water is too short, the air will not be completely saturated with vapor. There are various ways in which this state of partial saturation can be expressed in practice. One of the most commonly used Indices is relative saturation or relative humidity. It is defined as 10!Pi.0 (1-28) relative saturation =12 1 Introduction Table 1-4. Equilibrium vapor pressure of pure water ‘Vapor pressure Vapor pressure rr in. He Tin 32 0.180 0 0.248 50 0.363 cy oz 70 0.739 2 3.032 90 1.422 100 1.932 no 2.596 120 3.446 130 4.525 140 5.881 150 7.569 160 9.652 0 12.199 180 15.291 190 19.014 200 23.467 11.526 212 29.922 14.696 20 34.992 17.186 230 42.308 20.719 240 50.837 24.968 250 woms 29.85 HS 1267.98 260 72.134 35.4008 120 1499.14 270 85.225 41.858 1s 1740.93, 280 100.18, 49.203 130 2026.36 2011719 37.587 135 2347.26 300 136.44 67.012 Sources: Data from AIP (reference 2) and Keenan and Keyes (reference 3) where Py,o is the partial pressure of water vapor in the gas mixture and Ph,o is the partial pressure of water vapor in the gas mixture ifthe gas mixture is saturated with vapor at the given temperature. The percentage relative humidity can be obtained by multiplying the relative saturation by 100. ‘Another important concept that must be considered is that of dew point. Let us suppose that the unsaturated air—water vapor mixture is slowly cooled. If the total pressure ofthe system is kept constant, then the partial pressure of the water vapor will not be changed by the cooling process. With continued cooling, however, the temperature will reach a value at which the partial pressure of water vapor in the mixture will become equal to the equilibrium vapor pressure of pure water. At this temperature, then, the mixture has become thoroughly saturated with water vapor, and any further cooling will only result in condensation of the water vapor. This temperature is known as the dew point of the gas mixture. The = 20.94(31.998) = 670.038 mass of Ar = 0,93(39.948) 37.152 mass of CO; = 0.03(44.009) 1.320, mass of Ne = (1.8 x 10°°)(20.183) = 0.036 mass of He = (5.2 x 10°4)(4,003) = 0.002 mass of Kr = (1.0 x 10°4(83.8) sass of Hz = (5.0 10°4)2.016) total mass of 100 moles of air molecular weight of sir (Max) 3596.169 2896. 1697100 = 28.962 For the purpose of calculating its density et us assume that air behaves ike an idea! go. This means that at STP the volume of 1 grmole of air is 22415 liters. The mass of 1 g-mole of air is 28.962 g. Therefore, .962/22.415 density of air (pu) 1.292 giliter at STP 1.292 kim at STP 1.292 mglens at STP ‘The weight-percentages of different components are computed as follows (2187.613/2896.169)100 = 75.534% weight-percent of O; = (670.038/2896.169)100 = 23.135% weight-percent of Ar = (37.152/2896,169)100 = 1.283% weight-percent of CO; = (1.320/2896.169)100 = 0.046% Wweight-percent of Ne = (0.036'2896.169)100 = 1.2 x 10-*9% ‘weight-percent of He = (0.002/2896.169)100 = 6.9 x 10% weight-percent of Kr = (0,008/2896.169)100 = 2.8 x 10~*% weight-percent of H, = (0.0001/2896.169)100 = 3,5 x 10° weight-percent of Nz * Example |-7. The molecules of diatomic gases tend to dissociate into atoms, and the degree of dissociation increases with rising temperature. Thus, at any given temperature the gas consists of a mixture of diatomic and monatomic particles. For simplicity, let us assume that the diatomic and monatomic portions of the gas obey the ideal-gas law. However. the gas mixture will not behave ideally, because the number of moles increases with increasing temperature. For the purposes of this analysis, let us define the degree of, dissociation, designated 6, as the ratio ofthe mass m, of the monatomic portion to the total ‘mass m of the gas mixture, That is, 5 = migim. (2) Prove that the equation of state of the gas is PY = (1 + &)(m/MRT where Mzis the molecular weight of the diatomic component. Assume that the gas obeys Dalton’s law. i (©) The table below lists data of PV/m for sulfur vapor at three different temperatures ‘Compute and show in a graph the degree of dissociation as a function of tomperature.ee 16 1 Introduction 100): 1000 1200 1400 Vim (kg): 1.654% 10° 1.916 x 10° 2.188 x 108 (2) Let us suppose that the total pressure, volume, and temperature are P, V. and 7, respectively. Let m and ny denote the number of moles of monatomic and diatomic feseour species, respectively. Let m, and m, be their masses and M, and M; be their ‘molecular weights. Therefore, ny = m/My and m= [Ma Let P; and P, denote the partial pressures of monatomic and diatomic species, respective: iy. Because individual components obey the idesl-gas law, PIV © nT = (omy/My)RT and PY = mRT = (m2/M2)RT ‘The total pressure, according to Dalton's Law, is given by PV = RT(om/My) + RT(m/M2) “The equation of state for this system thus becomes PV = RT(mi/My + ma/Ms) Moreover, M; = 2M. Substitution yields PY = (RT/Mz)(om +m, +m) I is given that m= m tm and 6 = m/m Substitution yields PY = (RT/M:)(m + 8m) or PV = (RTm/M:(1 + 8) ‘This is the required result, Rearranging the terms in this equation, (PV/m)(Ma/RT) (6) For the dissociation of sulfur dimer into sulfur monomer, that is, (8) = 25(8), we have My = 64 kglke mole, R= 8334.3 Mkemole-"K. (i) Att = 1000°C or T = 1273°K, 1+ 8 = (1.654 x 10°)[64i(8314.3 x 1273)] = 1 + (L414 x 10~4) Laid x 10+ 2) Att = 1200°C or T= 1475°K, 1+ 5 = (1.916 105)[64i(8314.3 x 1473)] = 1 + (1.26 x 10) 1.26 x 107? 00°C oF T = 167K, (2.es x r0}fu(enia3 « 1673) = 1 + (6.714 « 10° 6.714 x 10-9 ‘The degre of dsoiation increases with temperature, Figure 1-7 shows the degree of Goon ata fieton of temperature +8 @au Example 1-8. The moist blast used in an iron blast furnace contains 7.2 grains of water ‘vapor per cubic foot at 77°F. Determine the temperature to which the blast must be preheated in order that its relative saturation will become 0.12. Consider 1 fof moist blast as the basis.Problems Ww Figure 1-7. Degree of dissociation, 8, shown as a function of temperature mass of water vapor = 7.2 grains = 1.029 x 1073 Ib . pound-moles of water vapor = (1.029 * 10"2)/18.016 = 5,709 X 10-5 . Prov = myoRT V = Lifts R= 1545.45 felbtb-moje 98.35°K = 536.7 5.709 x 1078) 1585.45)(536.7) = 47.38 tit? 7 rom Hg or 0.67 in, Hg relative saturation = 0.12 = 17/Piyo : Phyo © 141.72 mam Hg or 5.58 in. Hg Referring to Table 1—4, we find that the temperature corresponding to this vapor pressure, is 138, PROBLEMS 1-1: The pressure in an evacuated vessel was recorded as 1.2 dyneslem?, Express this value in microns of mercury at 25°C. 1-2: An open-end manometer connected to a tank indicates 28.56 in, Hg at 25°C. ‘The barometer reading is 14.583 psia. The density of Hg is 13.59 glem?. What is the pressure inside the tank? 1-3: Compute the missing temperatures in the following table: Ov OO © © @ ‘C659 — = = 3380 *K— = 9m = 6s — F 456.— — 16646 — oa 1-4: The fux of radiant energy emitted by # black body is elven by Q= or - TH) where Q is the flux of radiant energy (ergs/em?-see), «ris the Stefan-Boltzmann constant [5.735 x 10? ergsiem?-sec(*K)*}, T is the temperature of the hot black body (°K). and 7, is the temperature of the surroundings (°K). What is the value of o in Bru! fhe-CR)"? 1S: How many gram-moles are there in (3) 100 g of aluminum trichloride (AICI), (&) 130.74 g of zine metal (e) 1 kg of metallic gold, and (4) 24 Ib of calcium fluoride (Car? _18 1 Introduction 1-6: Determine the number of pound-moles present in 100 Ib of each of the following substances: (a) feric oxide (Fe3Os), (b) magnesium carbonate (MgCO3), (c) nickel chloride hexahydrate (NiCl-6H,0), (6) aluminum metal, and (e) titanium dioxide (Ti0»). 1-7: A certain mixture of carbon monoxide and carbon dioxide weighing 20 g occupies 8 ‘volume of ISiiters at 25°C and I atm pressure, Calculate the composition of the mixture (a) in mole-percent and (b) in weight-percent 1-8: The composition by volume of a gas mixture is as follows: 12.4%, COy; 8.3%, CO; 6.1%, O3; 62.2%, Nzi and 10.4%, HO. Calculate (a) the average molecular weight ofthe gas mixture, (b) the composition ona dry (HO-free) bass, and (c) the composition ofthe moist gas on a weight-percent basis. 1-9: A lead concentrate has the following analysis by weight: PDS, 62.696; FeS, 21.8%; Zn, 3.9%; and SiO>, 11.7%. Calculate the analysis ofthe concentrate on a mole-percent basis. 1-10: A tankina factory silled with sir from a high-pressure line, and at the conclusion of the filling process the pressure and temperature in the tank are 120 psia and 150°F. Ifthe tank isleft standing for several days, what wll be the final pressure? The temperature inthe factory is maintained at 70°F. Assume that sir behaves like an ideal gas, 1-Ul: Calculate the pressure in atmospheres exerted by 3 g-moles of sulfur dioxide confined to 10 liters at 350°C (a) using the ideal-gas law and (b) using the van der Waals equation. 1-12: A constant-volume gas thermometer of volume 1 liter contains 0.05 g-mole of & gas, It is customary to assume that the ges obeys the ideal-gas law, but, more exactly, 1 grmole of the same gas obeys the van der Waals equation: (P + 0.8/V7)(V ~ 0.03) = 0.082067 where 7°K is the absolute temperature, and P and V are measured in atmospheres and liters, respectively. By how much will the temperature measurement bein error at 24°C? 1-B: The solubility of nitrogen gas in liquid iron at 1600°C and 1 atm pressure is 0.0451 wt.% (Trans. Met. Soc. AIBE 218:1088, 1960) Calculate the volume of nitrogen dissolved by 1 kg of molten iron under the specified conditions. Express the volume in cubic centimeters at (2) STP and (b) 1640C and 750 mm He pressure. 1-14: In the electothermic smelting process for zine, product gases containing 47 vol.% Zine and 53 vol.% carbon monoxide are sent to the condenser at a temperature of 900°C. The pressure can be assumed as 1 atm, Calculate the volume of gases entering the condenser, in cubic feet, per ton of zine produced. Assume that zinc losses during the condensation process are negligible. 1-15: The average grade of copper ore deposits in the United States is expected t0 decline t0 0.5 w.% by the year 1990. Ifthe anticipated annual consumption of copper in that year i 2.7 million tons, then, assuming that two-thirds of the anticipated demand will be met by freshly mined copper or, caleulate the quantity of copper ore that must be processed per year. Assume tha the overall recovery of copper is 84% Ifthe residue (cailings) from the processing operations were to be spread in a 10-f-deep bed on fat lan, calculate the acreage required to contain. The average speciic gravity ofthe mined ore is 2.05 1 acre = 43,560 f°. 1-16: Hydrogen sulfide, when heated, dissociates into hydrogen and sulfur acording to the equation H,S(g) = Ho(g) + 0.582(e) ‘The dissociation of diatomic sulfur into monatomicsulfur can be neglected (Example 17). Initially the system consists of ny moles of HS gas at 25°C and I atm, The temperatureeed References 19 of the gas is raised while keeping the pressure constant at 760 mm Hg. The degree of dissociation, a, of HS is defined as the ratio of the moles of HS decomposed to the initial moles of HS in the system: a = (mo ~ n)/no, where m is the number of moles of undecomposed HS at temperature T°K. (@) Show that the equation of state of the gas is PV = mol + 0Sa)RT ‘Assume that the gas obeys Dalton’s law of partial pressures. (b) The table below lists data on PV/no, for hydrogen sulfide, at four different tempera tures. Compute a at each of these temperatures, and show in a graph the temperature dependence of the degree of dissociation, Temperature (°K): 102311031338 1408, PV ina Gigmole): 87409570 12,500 13,445 Each component gas is assumed to obey the ideal-gas law. 7 1-17: Assuming that dry air contains 79% Np and 21% Oz by volume, compute the density in grams per liter of moist air at 25°C and 1 atm pressure (a) when the relative humidity is 60% and (b) when the relative humidity is 100%. The vapor pressure of water (Table 14) at this temperature is 23.76 mm He, 1-18: The composition by volume of gas mixture in a zine retort at 1100C and 780 mm Hig pressure is 45% Zn, 53% CO, and 2% No. Determine the zine “dew point” of the gas mixture as best you can given the following data for the equilibrium vapor pressure of pure liquid zine (Pn) eC: 750 760 70 780 790 800 810 820 830 840 850 Poa (mm): 128-141-161“ 182 -206-«-233—«263.—«-29S-«331-—STL- ad REFERENCES 1. D. M. Himmelblau, Basic Principles and Calculations in Chemical Engineering, 3tded., Prentice-Hall, Englewood Cliffs, N.J., 1974 2. American Instinute of Physics Handbook, 2nd ed., edited by D. E. Gray, McGraw-Hill, New York, 1963, 3.1. H. Keenan and F. G. Keyes, Thermodynamic Properties of Steam, Wiley, New York, 1936,2 STOICHIOMETRY: MATERIAL BALANCES IN METALLURGICAL PROCESSES 2.1 Stoichiometry ‘The mass and volume relationships between the reactant and product species partaking in a chemical reaction constitute the principles of stoichiometry. As an illustration, let us consider the following reaction: Fess) + 4CO(g) = 3Fe(s) + 4CO,(8) Q-1a) DISSE + x2) = Ox SS859 + 4 x4D (2-16) The relationship between the masses of various species involved in reaction (2-12) is-given by equation (2—Ib). By making use of the atomic weights of the clements involved, similar equations can be developed for other reactions. Because 1 g-mole of a gas or vapor behaving ideally occupies a volume of 22.415 liters at STP, the foregoing reaction can also be written as Fe;O4(s) + 4CO(g) = 3Fe(s) + 4C0,(g) DMS q+ (4 22.415 liters) = (3 % 55.85 g) + (4 X 22.415 liters) ‘These relationships are very useful in solving problems. ‘The factors 1, 4, 3, and 4 appearing in equation (2~1a) are known as sioichio- metric coef ficients. A generalized treatment of the subject is facilitated by desig- nating the reaction components as follows:!~? Ry: FesOz, Rx: CO, Rs: Fe, and Re: COs Equation (2~1a) becomes 3Rs + 4Ry~ Ry ~ 4Ry = 0 2-2) Let a, az, as, and a denote the stoichiometric coefficients of species Ri, Ro, Rs, and Ry, respectively. Additionally, let the coefficients of the reactant species be negative and those of the product species positive. Equation (2~2) becomes ZaR,=0 (2-3) where a, = -1,a; = ~4, a3 = 3, anda, = 4 The absolute values of the stoichiometric coefficients are not as significant as their relative magnitudes; for instance, one may readily choose the coefficients as/ 4, 1, ay/a4, and 43/ag to express reaction (21a). Example 2~1 illustrates the application of stoichiometric principles. 20- t—~—S—S 2.2 Law of conservation of mass 21 Figure 2~1. Schematic representation of a flow system with fluid input at plane 1 and fluid output at plane 2. 2.2 Law of conservation of mass ‘The mass of an isolated system remains constant irrespective of the changes occurring within the system. This statement, known as the law of conservation of ‘mass, forms the basis of material balance calculations. To illustrate the applica- tion of this law, let us consider the open system shown in Figure 21. This system hhas a volime V and an initial mass mo. Mass is transferred into and out of the system: if the transfer rates are unequal, then mass accurnulates within the system itself. The mass balance over the volume V can be expressed as follows: Fate of input _ rate of output , rate of accumulation of mass of mass of mass Over a short interval of time, &1, this becomes WigBl = HoysSt + BW @-4) Where Wig is the rate of input of mass, oy isthe rate of output of mass, and is the mass accumulated in the interval 6. On dividing both sides of this equation by & and taking the limit as 6¢— 0, we have dw/dt = vig ~ vipy:: unsteady-state operation @-5) Material balance equations similar to equation (2-5) can be written for each of the components involved in the process. The components chosen may be simple compounds or elements. Thus, for components 1, 2,3,..., we have dwi/dt = (inh ~ Qouds dwa/dt = (Hig)a ~ Qoule dws/dt = (ving)s ~ Qbou3s «+» The foregoing equations apply to systems with a single input stream and a single output stream. For a system with multiple input and output streams, the material balance equation for the ith component becomes dw,/dt Ein). ~ Eo) e-6) For steady-state operation, the quantity on the left side of equation (2~6) is nil, so that we have22 2. Material balances in metallurgical processes Yin), = Vou, : ae al en or Cin) + (ing) BF = Wows) TF Ohad) IF where the superscripts I, II, . . . refer to the input streams and the superscripts I’, TV, .. refer to the output streams. For a batch process, the materials to be processed are all charged at once, and the products are discharged at the termination of the process. The material balance for the ith component in such a process is given by Z(Hin), = EWouds Bees Hoe 0-8) in) (Win) + = = oud + oud + ‘where (ig)! i the mass of component iin the 1 input stream and (Woy)! is the mass of component iin the I’ output stream, and so forth For chemically reacting systems, in addition to the law of conservation of mass, two other laws must hold good: 1. Law of definite proportions: A given chemical compound always contains the same constituent elements in the same weight proportions. (There are some i exceptions to this law. A well-known example is copper sulfide, whose compo- i sition can vary from Cu, 7S to Cuz.S. Materials in which the atomic ratio 4 varies are called nonstoichiometric compounds.) 2. Law of multiple proportions: If two elements can form more than one com- pound, then the respective weights of one clement that combine with a given ‘weight of the other are in the ratio of small whole numbers. Example 2~2is concerned with the reduction of a nonstoichiometric compound. 2.3 Method of calculation ‘The daily feed to a reactor consists of A tons of ore, B tons of blast, Ctons of coke, and D tons of flux. The species present in the feed materials arc as follows: Ore: Fe,O3, FeS, MnOz, P20s, AlO3, Si02, H20 Blast: Nz, O2, H2O Coke: C, Fe20s, FeS, Al,03, SiOz, HzO Flux: CaCOs, Fe;0s, SiOz, HzO ‘The products from the reactor amount to U tons of metal, V tons of slag, and W tons of gases per day. The species in each of these materials are as follows: Metal: C, Fe, FesC, FesP, FeS, Mn, Si Slag: AlOs, CaO, CaS, FeO, MnO, SiO Gases: CO, CO, Hs, No, HzOMethod of calculation B Table 2-1. Compositions of materials ‘Weight-percent of element NG apes ° Gee Se pees ke eee nee say a Us ee oe ar The compositions of materials are usually reported in weight-percentages of species present. Because none of these species is immutable, the formulation of mass-balance equations on the basis of species can run into formidable obstacles, especially when the details of the process are not clearly spelled out. Ifthe process details are not reported, the recommended procedure is to set up mass-balance equations for the constituent elements. In the present example these are Al, Ca, C, Fe, H, Mn, N, O, P, S, and Si, Let a), b;, and so forth denote the weight: percentages of the th element in the ore, blast, and so forth. A complete listing of the weight-percentages of the constituent elements in each of the materials is givenin Table 2-1. Inorderto simplify the formulation, the following assumptions have been made: (1) Metal contains no Al, Ca, H, N, or O. (2) All the P in the feed enters the metal. (3) S is partitioned between the metal and the slag. (4) The gases contain no metal-bearing species. The mass-balance equations are set up as follows: Mass balance for Al (daily basis): ayiA + aC = va ‘Mass balance for Ca (daily basis): de4D = ve,V Mass balance for C (daily basis): ccC + deD =ucl + weW Mass balance for Fe (daily basis): dpe + CreC + dreD =Upel! + UpeV ‘Mass balance for H (daily basis): ayA +,byB + caC + dyD =wuW ‘Mass balance for Mn (daily basis): axiyA = ty4qU + DyiaV Mass balance for N (daily basis): byB = wxW Mass balance for O (daily basis): ag + boB + coC + doD = voV + WoW Mass balance for P (daily basis): ap =upU ‘Mass balance for S (daily basis): agA°* CsC = sl! + vsV Mass balance for Si (daily basis): aA + ¢5\C + dgD = ug) + vsV ‘There are altogether 11 simultaneous equations that can be solved for 11 unknown quantities. Had there been n independent-element mass-balance equations, then n unknowns could have been evaluated. The unknown quantities can be the weights (A, B, etc.) or analyses (a;, etc.) or combinations of both.24 2° Material balances in metallurgical processes Figure 2~2. Schematic diagram of an iron blast furnace, Output? Sintered ore, pellets, mill Flue dust (withthe top gases) + scale, serap, open-heart slag Flux: Limestone, doiomite Fuel: Coke Liquids | Pig iron slag Gases Hot blast air, moisture), oxygen enrichment, Blast furnace or top gas natural-gas injection, coal or oil injection upward movementihrough the blast furnace, | = downward movement tkroughthe blast furnace. 2.4 Blast-furnace charge-balance calculations Familiarity with the technique of applying the law of conservation of mass to practical situations can be gained through solving a succession of problems. Let us begin with problems related to the iron blast furnace; at present, this furnace is the principal means of producing molten iron from iron ore. Figure 2~2 shows a schematic diagram of the blast furnace, and Table 2~2 provides «list of materials entering and leaving the furnace. The “charge,” consisting of iron ore or equiva- lent (pellets, sinter), limestone (and dolomite) flux, and coke, is fed at the top. 2 atpalin 2.4 Blast-furnace charge-balance calculations 25 ‘The oxide ore is reduced to metal by the ascending gases (CO, H,) that are generated within the furnace, at the tuyere level, by the combustion of coke with hot blast delivered through the tuyeres. The furnace can be conveniently divided into four zones: the stack, the bosh, the combustion zone at the tuyere level, and the hearth, The physical-chemical processes occurring in each of these zones are discussed next. . Stack 1. Evaporation of uncombined moisture: H,0(1) = H20(g) 2. Dehydration of ore: Fe,OyxH,0 = Fe:03 + xH,0(g) 3. Reduction (much of the iron oxide reduction taking place in the furnace is actually brought about by gaseous reducing agents within the stack): 3Fe03 + CO (or Hz) = 2FesOx + CO; (or HO) Fes + CO(orH;) = 3FeO + COs (or HO) FeO + CO (orH) = Fe + CO; (or H,0) 4. Carbon-solution loss reaction: C + CO; = 2c 5S. Water~gas shift reaction: H,0 + CO = H; + CO, 6. Reduction of MnO3: MnO, + CO = MnO + CO; 7. Decomposition of flux: CaCO = CaO + CO; MgCO; = MgO + CO, Bosh 8. Direct reduction FeO + yC = Fe + (2y = 1)CO + (1 ~ y)COr 9. Carburization of iron: 2Fe + C = FezC 10. Slag formation: CaO + MgO + AiO; + MnO + FeO + SiO; = slag Tuyere level:, combustion zone 11. Combustion of coke: +050, = co °26 2. Material balances in metallurgical processes 12, Reduction of water vapor in the blast: C+ H,0 = CO +H, 13, Phosphorus formation: P,Os + SC = 2P + SCO 14, Manganese formation: MnO + C = Mn + CO 15. Silica reduction: SiO, + 2C = Si + 2CO Hearth 16, Slag—molten metal interaction: C+ (CaO) +S = (Cas) + CO(g) where C and $ denote the carbon and sulfur present in the’hot metal and (CaO) and (CaS) are the slag species. Examples2—3,2~4, and 2~5 illustrate the method of charge-balance calculations in the iron blast furnace. 2.5 Material balances in copper smelting and converting ‘The conventional practice makes use of a reverberatory furnace in which a charge of copper concentrates, converter slag, and flux are smelted to produce matte and an iron silicate slag. The matte contains Cu, Fe, and S and minor amounts of PbS, ZnS, and precious metals. During smelting, some of the sulfur in the charge gets oxidized to SO2, which leaves the furnace with the off-gases. The molten matte is, transferred to @ converter, where it is oxidized with air to blister copper. The converting of matte is a two-stage operation. During the first stage, the iron sulfide in the matte is oxidized to iron oxide, which by combining with the silica ux forms an iron silicate slag. FeS + 1.50, = FeO + SO, FeO + 2Si0; = FeO-2Si02 Because the converter slag contains an appreciable amount of copper, it is skimmed off and returned to the reverberatory furnace. The remaining liquid in the converter is essentially stoichiometric CuzS, otherwise known as the “white metal.” In the second stage of the converting operation, the white metal is oxidized to blister copper: Cu,$ + Oz = 2Cu + $0, At the completion of converting, the blister copper is transferred to an anode refining furnace. ‘The method of performing a material balance on a copper smelter is illustrated in Example 2~6, where the smelter is fired with natural gas, and the composition of the off-gases is also calculated, Example 2-7, on the other hand, deals with the 1——— 2.7 Unsteady-state operations: the basic oxygen process 2 converting of copper matte in a Peirce-Smith converter. The amount of SO3 in the off-gases is calculated as function of matte grade. Airis used to bring about the oxidation process in the converter. 2.6 Continuous copper-smelting processes Te conventional reverberatory smelting and converting prbcesses suffer from a number of disadvantages, the foremost among them being as follows: (1) The SO; content of the reverberatory off-gases is too weak to permit economical recovery of sulfur. (2) A sizable portion of the chemical energy of the charge is lost with the off-gases. (3) These are batch processes that do not readily lend them- selves to computer control. To improve the economics of sulfur recovery and to obtain greater smelter flexibility and better heat utilization, efforts were focusedon direct-converter smelting of copper concentrates using oxygen-enriched air.‘~* ‘These and other allied efforts gave birth to 2 new generation of Gopper-smelting, processes.”-° ‘The Noranda continuous smelting process” employs a reactor whose configura- tion is similar to that of the conventional Peirce-Smith converter except for @ raised hearth at one end (Figure 23). The concentrates and flux are fed to the reactor at one end. The smelting of the feed produces two layers: one of slag and the other of matte. Much of the heat required in the smelting process is generated within the reactor itself by the converting reactions. Additional heat is supplie¢ by the end burners. As the matte flows toward the discharge end, it is converted by the air injected through the tuyeres located along the length of the reactor. The ferrous sulfide in the matte is oxidized to ferrous oxide, which combines with the silica in the slag. As the white metal (Cu,S) reacts with the injected air, it separates into a sulfur-rich phase and a copper-rich (97-99% Cu) phase. ‘The latter has a higher density and settles into a sumplike depression in the middle of the reactor. The dynamic conditions existing in the molten bath seem to favor the formation of some copper-rich phase even before all of the ferrous sulfide in the bath is oxidized. The process generates a continuous stream of off-gases with @ high SO2 content well suited for the manufacture of sulfuric acid ‘The molten copper and slag are tapped off intermittently. The copper produced contains 1.5 to 2% S, a concentration somewhat higher than that present in the blister copper from the conventional process. The stag contains 10 to 12% Cu and 20 to 30% magnetite. Flotation of ground slag yields @ concentrate containing, about 50% Cu and tailings with 0.5% Cu. The siag concentrate is recycled. The oranda process is very flexible and can be readily adapted to produce a high: grade (70-75% Cu) matte that is subsequently converted to blister copper in a separate vessel. ‘The details of setting up a comprehensive charge-balance sheet for the Noranda copper smelter are considered in Example 2-8. The smelter was fired with bunker C fuel oil, and combustion was affected with air. 2.7 Unsteady-state operations: the basic oxygen process ‘The basic oxygen process can convert blast-furnace iron and scrap te carbon and low-alloy steels at low cost and at a high production rate. The first experimental_ 2.7 Unsteady-state operations: the basic oxygen process 29 Figure 2-4. Basic oxygen furnace (top- blown). (Adapted from J, Macnamara, T.R. Conway, and W.S. Suhay, in BOF Stel: ‘making, vol. 1, edited by J. M. Gaines, American lastitute of Mining, Metallurgical and Petroleum Engineers, Warrendale, Pa., 1974.) Figure 2-5, Removal of impurities during the blow in a basie oxygen 4 fumace. (Adapted from C. Bods worth and H. B. Bel, Physical Chemistry of tron and Stel Manufacture, 2nd ed., Longmans, London, 1972.) ‘g : (Slt %5, %P 101, %.6, 9M 0 3 10 5 20 Time, min basic oxygen furnace was constructed at Linz, Austria, in 1949. At Donawitz, Austria, the process was further investigated and improved. The process is sometimes referred to as the L-D process in recognition of its place of origin and ‘growth, Following its inception. the process grew rapidly, primarily at the expense Of the open-hearth process. One of the notable features of the basic oxygen process is its flexibility; itis an efficient method of producing steel regardless of the size of the furnace. Furnaces of nearly 400 tons capacity are now in use, and even larger vessels are under consideration. ‘The basic oxygen process isa batch process, andit operates at an unsteady state. The process uses pure oxygen to refine molten iron. The oxidation of the impuri- ties (C, Si, Mn, P, etc.) present in the molten iron provides the heat necessary to sustain the process. In fact, the process generates excess heat, permitting the charging of some scrap along with the molten iron. ‘The basic oxygen furnace is a pear-shaped vessel (Figure 2-4) lined with magnesite or dolomite. Oxygen is delivered through a water-cooled lance. Several different types of lance designs are in use. The charge occupies but a small portion,30 2 Material balances in metallurgical processes of the total vessel volume. The charging operation is begun with the addition of lime. The hot metal is transferred to the vessel, and then the serapis added. After charging, the vessel is moved into an upright position, and the lance is lowered into the vessel. The lance nozzle is 1 to 2 m above the bath level. Oxygen gas is blown onto the surface of the liquid at a very high velocity. The oxygen jet penetrates the slag layer and interacts with the liquid metal. The high-speed action and the general agitation of the bath result in the formation of a metal-slag emulsion that in turn causes rapid refining. The operation, or the blow, as itis called, lasts about 20 min. The removal of the impurities during the blow is -hown in Figure 2S. The principal reactions are as follows: C+ WO,(g) = CO) Si + Ox) = SiOz Mn + %402(g) = MnO 2P + 402g) = P205 CO(g) + 40,{8) = COA(e) Fe{) + AOa{e) = FeO ‘The italicized species are in a dissolved state; the elements are part of the liquid metal, and the oxides are part of the slag. Not much sulfur is removed from the metal in the basic oxygen process. WORKED EXAMPLES Example 2-1. Pyrite, FeS, is @ naturally occurring mineral of iron-and sulfur. If the pyrite 93.6 wt% pure, withthe remainder an inert clay, how many kilograms of sulfur are present per ton of pyrite? If the pyrite is completely oxidized to FeO; and SO;, what are ‘ie amounts of these products per ton of pyrite? Consider 1 ton of impure pyrite as the basis, mass of FeS, mineral = 936 ke 1 gmole of FeS, contains 2 g-atoms of sulfur molecular weight of FeS) = 119.85 119.85 kg of FeS: contains 2 * 32 kg of sulfur How much sulfur is in 936 kg of FeS;? The amount of S present in the pyrite ore is 500 kg, ‘The oxidation of pyrite can be represented as follows: 2FeS + 5.503 = Fess + 4502 aesiees 187) 286 it of Fe,O; produced: — 623.6 kg amount ofFe;03 produced = ~~ = Ls 2 x 119.85 * 236 x 936 amount of $0; produced = =" — 999.64g Pe ni98s Example 2-2. Iron can be produced by the reduction of wustite, Feg ©, with carbon ‘monoxide: FeqsiO(l) + CO(g) = 0.94Fe(s) + COx(e) '_ a Worked examples 31 Calculate the weight of wustite required and the volume of CO gas consumed to produce J ton of iron From the foregoing chemical equation itis clear that to produce 0.94 X 55.85 kg of Fe, 68.499 kg of wustite and 1 kg-mole of CO gas are required. = SI _ 308 8k Z 0.94 x 55.85 t ‘One kilogram-mole of CO gas occupies 22.415 m? at STP, 2 CO consumed = — 0 x 1000 x 55.85 = 427 mac STP Example2~3. An iron blast furnace produced 2400 tons of pig iron per day. The analysis Cf the pig iron was 92.9% Fe, 4% C, 1.38% Si, 0.9% P, 0.8% Mn, and 0.02% S. The iron fore charged into the furnace contained 72.2% Fe;0;, 9.6% SiOz, 7.89 AlsOs, 6.2% H,0, 3.1% MnO, and 1.1% POs, The coke used contained 89% C, 89% SiOz, 2% AlLO3, and 1% FeS. The limestone flux was 96.5% CaCO, and 3.5% SiO;, The input rates of coke and limestone were 1800 and 1200 tons per day, respectively, Furthermore, 98.5% of all the iron enteting the furnace was accounted for by pigiron. Determine (I) the input rate of ore and (2) the output rate and composition of the slag. Assume steady-state operation, For steady-state operation, the conservation of mass yields input rate of the ith component = output rate of the ith component For iron, (ig) (0.722) 111.7759.7) + 18(55.85187.85) = 2400(0.9290.985) 50 (hg), = input rate of iron ore = 4462 tonsldey o ‘The slag-forming constituents are Al,Os, CaO, CaS, FeO, MnO, POs, and SiO;. All units are tons per day. total AIO; input to the furnace = 4462(0,078) + 18(2) = 384 All of this AlgO, is accounted for by the slag. total sulfur input to the furnace sulfur in the pig iron = 24(0.02) = 0.48 sulfur going into the slag = 6.07 CaS in the slag = 6.07(72/32) = 13.7 total CaO input to the furnace = 1200(0,965)(0.56) = 648.5 amount of CaO converted to CaS = 13.%(5672) = 10.6 amount of CaO going into the slag = 637.9 amount of iron slagged off = 24(92.9)(1.5198.5) = 34 amount of FeO going into the slag = 34(71.85/55.85) = 43.7 total Mn input to the furnace = 4452(0.031)(S4.9470.94) = 107.2 amount of Ma in the pig iron = 24(0.8) = 19.2 amount of MaO going into the slag = 88(70,94%54.94) = 113.6 total PsOs input to the furnace = 44,62(1.1) = 49.1 total phosphorus input to the furnace = 49.1(62/142) = 21.6 Phosphonis output asa constituent of pigiron = 21.6 18(32/87.85) = 6.55 ‘Thus, no phosphorus enters the slag. total SiO input to the furnace Si in the pig iron 44.62(9.6) + 18(8) + 12.5) 24(1.38) = 33.1 : 14432 2. Material balances in metallurgical processes amount of SiO reduced to metal = 33.1(60.1/28.1) = 70.8, amount of SiO; going into the slag = 543.6 rate of output of slag = 1736.5 tonsiday Slag composition: 22.12% AlsOs, 36.74% CaO, 0.79% CaS, 2.52% FeO, 6.53% MnO, sind 31.3% SiO, + Example 2—4. The daily charge to an iron bast furnace consists of 3600 tons of hematite ‘ore, 2000 tons of cake, and limestone ux suficent to produce a slag containing 35% SiOz, Ore: 74.4% Fes0s, 9.8% SiOz, 0.9% PiOs, 3.4% MnO;, 4.3% AlLOs, and 7.2% H,0. Coke: 88% C, 8.5% SiOz, 1.6% FeS, and 1.9% HO. Limestone: 97.6% CaCOs, 0.8% ‘AlO,, 15% SiO, and 0.68% H,O. Pig iron contains 3.8% carbon. All ofthe phosphorus i in the charge enters the pig iron, and so do 40% of the manganese and 15% of the silicon in the charge. All ofthe sulfur and 1.2% of the ion in the charge are slagged off. The amount of blast per ton of coke charged is 3600 m? measured at 17°C and 1 atm. The . blast is preheated to a final temperature of 771°C, and its steam content amounts to 5 gim’. Assuming steady-state operation, (1) prepare a charge balance, and (2) find the ‘compositions of pig iron slag, and the top gas. In the following calculations, all weights are in tons, and all percentages are by weight, except where noted otherwise For steady-state operation, equation (2~7) applies. In other words, input rate of Fe = output rate of Fe Fe in the hematite ore = 3600(0.744)(111.7/159.7) 2678(111.7/159.7) = 1872 Fe as FeS in coke 20.3 total Fe input tothe furnace Of the total Fe, 1.2% is slagged off as FeO. a amount of Fe slagged off = 1.2(18.923) = 22.7 amount of FeO in the slag = 22.7(71.85/55.85) = 29.2 amount of Fe entering pig iron = 1869.6 total P input to the furnace = 32.4(62/142) = 14.2 No phosphorus enters the slag, 42 122.4(54.94186.94) amount of P entering pig iro total Ma input to the furnace Of this total amount, 40% enters pig iron. amount of Mn entering pig iton = 77.4(0.4) = 31 ‘amount of Mn going intothe slag = 46.4 amount of MnO in the slag = 46.4(70.94/54,94) = 59.9 ‘The amount of flux used is computed as follows. Gi, in tons per day, denotes the input rate of flux to the fumace. total SiO; input to the furnace = 523 + 0.017 total Si input to the furnace = (523 + 0.01G;)(28.1/60.1) OF this silicon, 85% enters slag as SiO, amount of SiO; going into the slag = 444.5 + 0.00856, ‘The other components in the slag, besides SiOs, are Al,Os, CaO, CaS, FeO, and MnO, total CaO input to the furnace = G,(0.976)(0.56) = 0.54666, j - we abe |Worked examples 33 Of this CaO, a small portion is converted to Cas, total § input to the furnace = 32(32/87.85) = 11.7 None of this sulfur enters pig iron and all of itis converted to CaS. ‘amount of CaS going into the slag = 11.7(72/32) = 26.3, amount of CaO converted to CaS = 26.3(56/72) = 20:5, 1 amount of CaO going into slag = 0.54666 ~ 20.5 amount of Al,Os going into slag = 154.8 + 0.0086, amount of slag formed = Al,O; + CaO + CaS + FeO + MaO + SiO; total amount of slag = 694.2 + 0.5631G, Because SiO; constitutes 35% of the slag, we have 4445 + 0.00856, = 0.35(698.2 + 0.56316) . Gj = input rate of the fux amount of CaO going into slag = 564.0 ° amount of iO; going into slag = 453.6 2 amount of SiO; reduced to Si = 80.1 amount of Si entering pig iron = 80-1(28.1/60.1) = 37.4 amount of Al going into slag = 163.4 amount of Ca tied up as CaS = 20.5(40056) = 14.6 amount of © freed by CaO->Ca8 conversion = 14.6(16/40) = 5.8 We now calculate the amount of carbon entering pig iron; denote this quantity by 4. 1952.2 + q total mass ofpigiron . q = 0.038(1952.2 + 4) . Solving for g, we find 4 = amount of carbon entering pig iron = 77.1 Blast calculations total amount of bast = 3600(2000) = 7.2 x 10 m? volume of preheated blast = (7.2 x 10*)(1044/290) = 25.92 « 10° m? steam content = (25.92 x 10P)(5 x 10°) = 129.6 tons In 1 m® of preheated blast: mass of H30 = 5 g, mi,0 (S/18) grmole,V = 1000 titers oRT, where T= 1044°K (0.0238 atm = 18.1 mm For ideally behaving water vapor, Pu,oV Pao (S118)(0.08206)(1048/2000) Dry air contains 21 mol% Oz, 78 mol% No, and 1 mol%e Ar, Therefore, Po, = (760 ~ 18.1)(0.21) 155.8 mm; Py, = $78.7 mm; Pa, = 7.4 mm Using the ideal-gas law, we can find no, = 2.392 gmoles, ny, = 8.884 g-mol 0.114 g-mole , ln the preheated blast ‘logrammoles of O2 = (25.92 x 108)(2.392 x 107%) = 62.07 x 10? kilogram-moles of N; = (25.92 x 10°)(8.884 x 10-*) = 23.04 x 10 hilogram-moles of Ar = (25.92 x 108)(0.114 x 107%) = 2.954 x 10° mass of oxygen in the blast = (62.07 x 32) = 1986 tons { _ abTe 34 2 Material balances in metallurgical processes 6571 tons 8686.6 tons ‘mass of nitrogen and argon* in the blast mass of moist blast (inclusive of steam) Oxygen from the solids in the charge oxygen entering the furnace as Fe;O; = 2678(48/159.7) = 804.6 ‘oxygen tied up in the FeO of slag = 29.2(16/71.85) = 6.5 oxygen of Fe;0; going into gases ~ 798.1 , oxygen of P30; going into gases = 32.4(80/142) = 18.3 oxygen entering the furnace as MnO; = 122.4(32/86.94) = 45.1 ‘oxygen tied up with MnO of slag = 59.9(16770.94) = 13.5 oxygen of MnO; going into gases = 45.1 ~ 13.5 = 31.6 ‘amount of SiO; reduced to metal = 80.1 oxygen of reduced SiO going into gases = 80,1(32/60.1) = 42.6 oxygen from CaQ+Ca8 conversion going into gases = 5.8 Orygen from the gases fed to the furnace ‘oxygen from the water vapor in the blast = 129.6(16/18) = 115.2 tons Combustion of carbon at the tuyeres amount of carbon charged into the furnace = 1760 ‘amount of carbon going into pig iron = 77.1 ‘mass of carbon burned at the tuyeres = 1682.9 mass of oxygen available for combustion = 2997.6 fi ‘Thé combustion of coke produces CO gas, a portion of which is subsequently oxidized to COr gas. mass of oxygen required by C->CO conversion = 1682.9(16/12) = 2243.9 ‘mass of oxygen in excess of that required for CO formation = 753.7 tons ‘mass of CO formed at tuyeres = 3926.8 tons mass of CO oxidized to COs gas = 753.7(28/16) = 1319 net amount of CO gas formed = 3926.8 - 1319 = 2607.8 amount of CO; gas formed by oxidation of CO gas = 2072.7 . ‘amount of CO; gas released by calcination of limestone ~ 1044.3(44/100) = 460.1 net amount of CO. gas formed = 2532.8 net amount of hydrogen formed = 129.6 ~ 115.2 = 14.4 niet amount of water vapor in top gas = 303.6 ret amount of nitrogen in top gas = 6571 Conversion of these masses into kilogram-moles is carried out: kilogram-moles of CO gas = (2607.8/28)(10°) = 93.13 x 10° Kilogram-moles of CO: gas = (2532.8/44)(10°) = 57.55 x 10° Iilogram-moles of Hy gas = (14.4210) = 7.20 = 10° kilogram-moles of HO gas = (308.6/18)(10) = 16.87 10° Iilogram-moles of Ns gas = (6571/28)(10) = 234.7 x 10° ‘The complete charge balance is given in Table 2~3. The compositions of pig irom, slag, and the top (blast-furnace) gas are computed as follows: ‘Henceforth, argon will be included in the igure for nitiogen. .ieee Worked examples 35 Table 2-3. Charge balance (in tonsiday)* Sotits Ore: 3600 Fez, 2678 Fe 1849.3, FeO 29.2 0798.1 SiO, 353 si374 SiO; 272.9 006 POs 32.4 P42 - O183 MnO, 122.4 Mn 31.0 MnO $9.9 0316 ALO 154.8 = AlOs 154.8 HO 259.2 = = HO 259.2 Coke: 2000) 1760 cm = + 1682.9 SiO, 170 = SiO, 170 ° Fes 32 Fe 20.3 sin7 H,0 38- - = H,0 38 Flux: 1070 CaCO; 1044.3 = C20 564.0; CO; 460.1; CaasCa$ 14.6 O from Ca0.5.8 AhO, 8.6 - ALOs 8.6 SiO, 10.7, - SiO, 10.7 H,0 6.4 - _ H,0.6.4 Gases Blast: $686.6 0 1986 S = 0 1986 N67 = = Nes71 0 129.6 = = H144; 01152 "The charge balance developed here follows the approach of Butts (reference 10). Pig iron (wt.%) Slag (w.%) Fe 1869,6(92.15%) AhOy 163.4(12.61%) CO (22.74%) C 77.1 G.80%) CaO 564.0(43.51%) —CO4(14.06%) Mn 31.0 (1.51%) CaS 26.3 (203%) Hz (1.76%) P 142 (0.70%) FeO 29.2 (2.25%) HO (4.12%) Si 37.4 (1.84%) — MnO $9.9 (4.62%) ——Np_(57.32%) SiOz 453.6 (35.00%) ‘Top gas (vol.%) ‘Example 2-5. The daily charge to an iron blast furnace consisted of the following. Al percentages are by weight. - Pellets: 2400 tons 86% FeO, 9%6 SiO;, 0.69% CaO, 0.5% AlOs, 0.4% FeO, 0.4% MgO, 0.25% MnO, 0.089% P:0s, 0.01% FeS, 2.8% H;0 Siner: 2400 tons (6% FesOs, 14% FeO, 85% SiOs, 6% CaO, 2% ALOs, 1% MgO, 0.75% MnO, 0.1% P;0s, 0.05% FeS, 1.6% HO 736 2. Material balances Pluses Limestone: 315 tons 98.5% CaCOs, 1.8% MgCOs, 0.7% Fes, 0.5% Al,Os, 0.5% SiOz Dolomite: 375 tons 54.6% CaCO, 43.8% MgCOs, 0.6% Fez0s, 0.5% S103, 0.5% AhOs Fuel Coke: 1875 tons 87% C, 3.5% SiO3, 2.5% AlzOs, 1.5% FeS, 0.4% CaO, 0.1% MgO, 5% HjO “The amount of blast supplied to the tuyeres was 5.85 x 10®m"/day measured at 37°C and. ‘atm. The moisture content was 30 g/m? of nonpreheated blast. The solid particles carried away by the upward-moving gases were collected in the dust catchers. This fue dust ‘amounted to 65 tons/day and contained the following: 60% FesOs, 18.59% C, 8.5% CaCO, 8% SiOz, 3.5% MBCOs, 1.5% AlOs Allthe phosphorus charged, one-half ofthe Ma, one-seventh ofthe Si, an'one-tenth of the sulfur entered the pig irom, which also contained 93.5% Fe. Assume that no iron was lost in the slag, The blast-furnace operation was at steady state. (1) Prepare a charge balance. (2) Find the amounts and compositions of pig iron, slag, and top gases. (3) Find the fraction of carbon in the coke burned at the tuyeres. Mass balance for iron (tonsiday) input as pellets = 2064(111.7/159.7) + 9.6(S5.85/71.85) “= 0.24(55.85/87.85) = 1450.9 input as sinter = 1584(111.7/159.7) + 336(55.85771.85) + 1.265.85087.85) input with Nuxes = 4 9(111.7159.7) input with coke = 28.2(55.85V87.85) = 17.9 output with Bue dust = 39(111.71159.7) = 27.3 output with pg iron = 2814.8 amount of pig iron = 2814.8/0.935 = 3010 Mass balance for phosphorus (tonsiday) 96(62/142) = 0.42 2,4(62942) = 1.10 2 input with pellets input with sinter output with pigiron Mass balance for manganese (tons/day) 6(54.94/70.94) = 4.6 input with sinter = 18(S4.9400.94) = 14 total input of Mn = 18.6 amount of Mn entering pig iron = 9.3 amount of MnO going into the slag = 9.3(70.94/54.94) input with pellets 2 Mass balance for silicon (tonsiday) SiO; input with pellets = 2400(9/100) = 216 ‘SiOp input with sinter = 2400(8.5/100) = 204 : metallurgical processesere OO Worked examples 37 SiO, input with fluxes = 375(1/100) = 3.7 ‘SiO; input with coke = 1875(3.5/100) = total input of SiO. to the furnace = 489.4 amount of Si entering pig iron = (1/7)(489.4)(28.1/60.1) = 32.9 amount of SiO, going into flue dust = 65(8/100) amount of SiO; going into slag = 413.7 8.7 ‘Mass balance for sulfur (tonsiday) input with pellets = 0.24(32/87.85) = 0.09 input with sinter = 1.20(32/87.85) = 0.44 input with coke = 28.2(32/87.85) = 10.25 ‘output with pig iron = 1.08 sulfurentering the slagasCaS = 9.7 Mass balance for carbon (tonsdey) input of carbon with coke = 1631 ‘output of carbon with five dust = 65(18.5/100) = 12 ‘output with pig iron = 3010 = (Fe + P + Mn + Si + S) ‘output of carbon with gases = 1468.5 50.5 Mass balance for oxygen (considay) input of oxygen with FezOs of pellets = (2064 — 39)(48/159.7) = 609 input of oxygen with FeO of pellets = 9,6(16/71.85) = 2.1 input of oxygen with Fess of sinter = 1584(48/159.7) = 476 input of oxygen with FeO of sinter = 336(16/71.85) = 75 input of oxygen from the SiO, reduction = 32.9(32/28.1) = 37.5 input of oxygen from the MnO reduction = 9.3(16154.94) = 2.8 input of oxygen from the POs reduetion = 1.52(80/62) input of oxygen fromCaO—C sSconversion = 9.7(16/32) = 4.8, total input of oxygen from solids = 1210.5 tonsiday 8 Blast calculations on a daily basis volume of moist blast = 5.85 x 10° may ‘mass of moisture in the blast = (5.85 x 10°)(30 x 10°) = 175.5 tons volume of 1 kg-mole of H,O(g) at STP = 22.4 m? volume of 1 kg-mole of H,O(g) at 37°C = 22.°(310273) = 25.43 m? Volume of 175.5 tons of moisture at 37°C = (175.5 * 10°)(25.43/18) = 0,248 > 10" m°lday 5.602 x 10* miiday (6.002 x 10°)(273310) Volume of dry blast at 37°C and 1 atm volume of dry blast at STP At STP, 1 m? of dry air weighs 1.293 kg. ‘mass of the dry blast = 1.293(4934) = 6380 tons ‘ass of oxygen in the dry blast = 0.232(6380) = 1480 tons ‘ass of nitrogen in the dry blast = 0.768(6380) = 4900 rons ‘mass of the moist blast = 6380 + 175.5 = 6555.5 tons Coke reacts with the H,O(g) of ‘oxygen from the H;O() in the blast hydrogen from the H;0(g) in the blast 934 10° m* wet blast 175.5(1618) 175.5(2/18)38 2° Material balances in metallurgical processes oxygen input with the moist blast = 1480 + 156 = 1636 tons total input of oxygen = 1636 + 1210.5 = 2846.5 tons ‘oxygen required by C-+CO combustion = 1468,5(1612) = 1958 tons ‘oxygen in excess of combustion requirements = 888.5 tons amount of CO formed by combustion atthe tyeres = 3426.5 tons . ‘The excess oxygen oxidizes some of this CO to COn amount of CO oxidized to CO, = 868.5(28/16) ' amount of CO remaining ~ 1871.5 tons amount of CO; produced by oxidation = 2443.5 tons amount of CO; released by decomposing solids = 335.1 tons total amount of CO; produced = 2778.6 tons ‘The charge balance is shown in Table 2~4. The following are the amounts and com- positions of pig iron, slag, and top gases (see p. 39): i Table 2-4. Charge balance (in tons/day) a iquids output Input output Pig iron Slag Gases output i Solids | Pellets: 2400 Flue dust: 65 FesOs 2064 Feg0s39 Fe 1416 = 0 609 1 SiO, 216 SiO, 5.2 Si 32.9 SiO, 140.4 0375 i CaO 144 - - C20 144 = | Al;O3 12 ALO3 10 — AlzO3 IL - F096 = Fe75 ae O24 i MgO 9.6 = = MgO 9.6 = Ma0 6.0 = Ma 4:6 = O14 P:05 0.96 = P0482 = o0ss Fes 0.24 = Fe0.15;S0.09 — pie H,0 672 = a = #0 672 | Sinter: 2400 | Fe,03 1584 — Fe 1108. - 04% i} Fe0 336 = Fe 261 = O75 SiO; 204 = a SiO, 204 = C20 tat = = Ca as CaS 12.1; OfromC204.8 a0 127.1 ALO, 48, = = ALO, 48 = MgO 24 = = Myo 24 7 } MnO 18 _ Mn 4.7 MnO 12 ol P105 2.4 = Pil — O13 | Fes 1.2 - Fe0.76;S0.44 — ! #0 364 = = = H,0 384 Fluxes Limestone: 375 | CaCOs 362 CACO, 5.5 — cad 199.6 CO; 156.9 | | MgCO;68 — MgCO,2.3. — MgO 2.2 60323 | Fe03 26 = Fes fe O08Worked examples 39 ‘Table 2-4. (Continued) Solids Liquids output Input output Pig iron Slag Gases output ‘AL03 1.8 - = ALO18 t Si, 1.8 - - SiO2 1.8 = Dolomite: 375 CaCOs 208.7 — a C20 114.7 C0, 90 MgCO, 164 — = MgO 78.5 CO, 85.9 Fe.0,2.3 - Fes — 007 SiO; 1.8 - - SiO. 1.8 = ‘ALO; 1.8 - - ALO; 18 = Coke: 1875 C1831 cr C1505 = “c14685 SiO, 65.7 = = $10, 65.7 7 ALO; 469 0 — - ALO, 46.9 = FeS 28.2 = Fet7.9;$0.55 SasCas97 0 — 20 75 7 a C2075 = MgO 1:9 = . MgO 1.9 7 1,0 93.8 = = = H0 93.8 Gases Blast: 6585.5 0.1480 = = = © 1480 N 4900 = = = N 4900 1,0 175.5 0.156; H19.5 Pig iron (3010 tons/day) ___Slag (1136.5 tons/day) Fe mia 93.30% ALO, 1095 9.63% © 1803 sa0% CxO” 463.3 40-7698 Si 329 1.059% CS 28 192% Mn “93 030% MgO 1162 10.2306 Po 152 0.05% MnO 12.0 1.069% S108 0.035% Sid, 413.7 36.40%, Top gases (9769. tonsiéay) \cgrammoles _volume-percent co ws 19.16% 6H xI® 2052 CO, 2788 28.44% Gisx1e 1938 Hy 19.5 0.20% 9.75 x 10° 3.00 #0 199.4 2.08% 12.08 % 10° 3.40 Ny 4900.0 50.16% 175.0% 10 $3.70 To determine the fraction of carbon in the coke burned at the tuyeres we note that the consumption of carbon at the tuyere level proceeds in accordance with the following chemical equations C+HO =co+H,40 2 Material balances in metallurgical processes carbon reacting with the oxygen of the blast = 1480(12/16) = 1110 tonsiéay ccarbon reacting withthe water vapor ofthe blast = 175.5(12/18) = 117.0 tons/day total carbon in the coke = 1631 tons/day fraction of carbon burned at the tuyeres = 1227.0/1631 = 0.7520 ‘Example 2-6 At 2 Kennecott smelter in Utah, the daily charge to a reverberatory furnace consisted of 880 tons of concentrates, S0 tons of precipitate, 22 tons of fue dust, 35 tons of limestone, and 420 tons of converter slag. Partial compositions of the charge materials and of the reverberatory slag produced in the operation are given in ‘Table 2-5. The matte produced contained 41% Cu, 25% S, and 31% Fe, The furnace was fired with natural gas metered at a rate of 5525 mihr, measured at 21°C and 762 ram Hg. The gas analyzed, by volume, 88% CH,, 4% C:Hs, 3% CH, and 5% Hy and was burned with air, 8 vol. ein excess of the theoretically required amount. (1) Find the amounts of matte and reverberatory slag produced. (2) What fraction of the sulfur in the charge was oxidized in the smelting operation? (3) Prepare a charge balance for the furnace with respect to Cu, Fe, S, SiO;, CaO, and Al,Os. (4) Determine the amount land the composition of the off-gases. steady-state operatonis assumed. Allweghisarein ons. Letwandu be the respective amounts of matte and reverberatory slag produced. Mass balance for copper on a daily basis Cu in the concentrates = 880(0.259) « 227.92 Cu in the precipitate = 50(0.795) = 39.75 ‘Cu in the flue dust = 22(0.355) = 7.81 Cu in the converter slag total Cu input to the furnace Cu in the matte Cu in the reverberatory slag total Cu output from the furnace thus, 0.41u + 0.0040 ay ‘Mass balance for iron on a daily basis Fe in the concentrates = 880(0.221) = 194.48 Fe in the precipitate = $0(0.011) = 0.55 Fe in the flue dust = 22(0.163) = 3.59 Fe in the converter slag = 420(0.473) = 198.66 total Fe input to the furnace = 397.28 Table 2-5. Compositions of materials tres) HO SiO, Ca0_— AL Oy ‘Component (Wt) (0.9) (WIM) (7%) _wH.4) (WH) _ (wk. 96) Ce ee ey Cy ey ay Precipitate mS 1 1k 72d Flue dust 355 163 109 20 65) (18 Limestone 67 823 Converter sag 4S 47.307 264 19417 Reverberatoryslag 0.4 3821.0 S158 461 1 Worked examples 4 Fe in the matte = (0.31) = 031 Fe in the reverberatory slag = u(0.382) = 0.3820 total Feoutput ofthe furnace = 0.31u + 0.3820 thus, 0.31w + 0.3820 = 397.28 ® 461 Solving equations (1) and (2), we find w amount of matte produced amount of reverberatory slag produced Mass balance for sulfur on a daily basis Sin the concentrates = 880(0.275) Sin the precipitate = 50(0.011) S in the flue dust = 22(0.109) Sin the converter stag = 420(0.027) total input to the furnace = 256.29 Sin the matte = 713.5(0.25) = 178.38 S in the reverberatory slag = 461(0.01) = 4.61 amount of S oxidized to $0; = 256,29 ~ 182.99 = 73.3, fraction of Soxidized in smelting = 73,3/256.29 = 0.286 ‘Mass balance for sitica on a daily basis SiO in the concentrates = 880(0,066) = $8.08 SiOz in the precipitate = $0(0.011) = 0.55 SiO; in the flue dust = 22(0.29) = 6.38 SiOz in the limestone = 35(0.067) SiOz in the converter slag {otal SiO input to the furnace ‘SiO, in the reverberatory slag = 461(0.371) = 171.03 SiQp in the matte = 178.24 ~ 171.03 = 7.21 ‘SiO; in the matte = 7.217.135 = 1.01% Mass balance for lime on a daity basis Ca0 in the concentrates = 880(0.003) = 2.64 C20 in the flue dust = 22(0.065) ='1.43 C20 in the limestone = 35(0.523) = 18.31 C20 in the converter slag = 420(0,019) = 7.98 total input to the furnace = 30.36 (CaO in the reverberatory slag = 461(0.058) = 26.74 CaO in the matte = 30.36 ~ 26.74 = 3.62 %CaO in the matte = 3.627.135 = 0.51% ‘Mass balance for alumina on a dally basis 880(0.019) = 16.72 22(0.018) = 0.40 ‘AhOs in the converter slag = 420(0.017) = 7.14 total AljOs input to the furnace = 24.26 ‘AlOs in the reverberatory slag = 461(0.086) = 21.21 AlOs with the matte = 24.26 ~ 21.21 = 3.05 eAlaOs in the matte = 3,05/7.135 = 0.43% e ab.2 2. Material balances in metallurgical processes Table 2-6. Charge balance (in tonsiday) Output Converter everberatory Concentrates Procipitate FiueDust Limestone slag Matte slag ce 2792 39.75 7.81 - 18.90 29254 1.86 Fe 194.48 oss 3.59 198.66 221.19 176.09 S 242.00 oss 2400 = 1317838461 SiO, 58.08 035 (6.38 235 110.88 721 17103 C0 268 = 1431831 7.98 362 26.74 ALO, 16.72 - 0.40 = 714 3.05 21.21 ‘The charge balance for the furnace is given in Table 2-6. Combustion of natural gas on a daily basis ‘ 525(24) = 13.26 x 10 m? amount of fatural gas This is corrected to obtain the amount at STP. volume of natural gas at STP = (13.26 x 10)(273/294)(762/760) = 12.35 x 10 m? volume of CHy at STP = 0.88(12.35 * 10") = 10.87 x 10° m* volume of GH, at STP = 0,04(12.35 x 104) = 4.94 x 10° m? volume of CH at STP = 0.03(12.35 x 108) = 3.71 x 10% m? volume of Hp at STP = 0,05(12.35 x 10") = 6.15 x 10° m? One kilogram-mole of gas occupies 224m? at STP Kkilogram-moles of CH, = 4853 kilogram-moles of CoH, = 220.5 kilogram-moles of GH = 165.6 kilogram-moles of Hy = 274.6 ‘The combustion can be represented by the following reactions: CH, + 20; = CO; + 2H,0 Gil, + 30; = 2CO> + 2,0 Gols + 7.50; = 6COp + 3H,0 Hy + 0.50; = H,0 ‘The following are the kilogram-moles of O; required for complete combustion of each of the species involved for the combustion of CHy = 4853(2) = for the combustion of C3H, = 220.5(3) = 6415 for the combustion of CyHg = 165.6(7.5) = 1242 for the combustion of Hy = 274.6(0.5) = 137.3 Oxidation of sulfur in the charge on a daily basis: ‘This may be represented as follows: S +0; = SO; amount of $ oxidized = (73.3 x 10°32 = 2291 ke-moles amount of O; required = 2291(1) = 2291 kg:moles 9706 TT—_—--— _ONONT,__ | Worked examples B 14,037.8 kg-moles 14037.80.21 = 66,847 kg-moles total amount of O; required total amount of sir required However, the air supplied was 8 vol.% in excess of the required amount. amount of airsupplied = 66,847(1.08) = 72,195 kg-moles excess air = 5348 kg-moles ‘Thus, at the completion of combustion, amount of Noi the off-gases = 72,195(0.79) = $7,034 kg:moles amount of Onin the off-gases = 5348(0.21) = 1123 kg-moles To calculate the total amount of COs in the off-gases, we need amount of COs from the combustion of CH, = 4853 kg-moles amount of CO from the combustion of C3H, = 441 kg-moles amount of COs from the combustion of Cg = 993.6 kg-moles , ‘mass of COs from the decomposition of CaCOs = 35(0.523)(44/56) = 14.38 tons amount of CO; from limestone = (14.38 x 10°)/44 = 326.9 kg-moles total amount of CO in the off-gases = 6614.5 kg-moles To calculate the total amount of H,O in the off-gases, we need amount of HO from the combustion of CH, = 9706 kg-moles amount of H:0 from the combustion of CH, = 441 kg-moles amount of HO from the combustion of C Figure 2-7. Percentage SO; in off-gases as a function of matte grade. Volume Percent of $0 i te OM-Coses —> co oe : ote ode ——» To calculate the amount of Sz produced, we need ‘803 produced by the oxidation of FeS = 1138.4 ~ 14.254 $0, produced by the oxidation of Cu;S = 7.874 ‘amount of SO> in the off-gases = 1138.4 ~ 6.389 total amount of off-gases = 11,940.8 ~ 91.86q Therefore, %S0, inthe offgases = 100(1138.4 ~ 6.38)/(11,940.8 ~ 91.869) This result is also shown graphically in Figure 2-7. * Example 2-8. A charge balance is to be drawn up for a Noranda copper-smelting Teactor. The daily charge to the reactor consisted of 1000 tons Gf copper concentrates, 240 tons of slag concentrates, 215 tons of siliceous flux, and $0 tons of dust. Chemical q ‘analyses ofthe charge constituents and of the copper product are given in Table 2-7. The ‘Aue dust collected from the off-gases amounted to 6% of the copper concentrates and46 2. Material balances in metallurgical processes Table 2-7. Chemical analyses Go Fe «SZ SQ, C20. AKOy-HO__Rest (0) ‘Component (wt. %) _(wt.%) (ot. 9%) (ort. %) (wt.%) (wE%) (wt %) (wt) _(wt.%) _ Seer ogee concentrates sig 5 9S 68 10 90 05 10 74 93 Fux — 64 20 ~ 60 S40 4.95.25, Dust uo 20 m0 20 60 13 16 0 91 Copper 7S 03S had the same analysis asthe “dust” inthe charge. The slag contained 27% S10, 9% Cu, and 1% S. The air supply to the furnace was set at 11 x 10° mr, measured at 20°C and 755 mm Hg. The moisture content of the air was 10 gim’. The fuel oil (bunker C) consumption averaged 3.65 mMfar. The specific gravity of the oil was 0.9861, and it analyzed 85.7% C, 10.5% H, 2.8% S, and 1.0% N. Compute (1) the amounts of blister copper and stag made per day and also the slag composition; (2) the fraction of sulfurin the charge oxidized to gaseous products; (3) the net oxygen transfer from the air to the liquid phases; (4) the amount and the composition ofthe off-gases; and (5) the charge balance. All weights, unless specified otherwise, are in tons. ‘Material balance for SiO; on a daily basis input of iO, with copper concentrates = 0.045(1000) = 45 0,090(240) 0,680(215) 0.060(50) total SiO; input to the furnace = 215.8 weight of the flue dust collected = 0,06(1000) = 60 ‘output of SiO; with flue dust = 0.05(60) = 376 amount of SiO, entering the slag = 212.2 This constitutes 27% of the slag ‘amount of slag made = 212.210.27 = 785.9 Material balance for Cu on a daily basis input of Cu with copper concentrates = 0,205(1000) = 205 input of Cu with slag concentrates = 0.485(240) =, 109.2 input of Cu with dust = 0.240(50) = 12 ‘otal Cu input to the furnace = 326.2 ‘output of Cu with flue dust = 0.340(60) = 14.4 ‘output of Cu with the slag = 0.090(785.9) = 70.73 amount of Cu entering blister copper = 241.07 ‘This constitutes 97.5% of blister copper ambunt of blister copper made = 241.07/0.975 = 247.3 Material balance for Fe on a daily basis input of Fe with copper concentrates = 0,270(1000) = 270 input of Fe with slag concentrates = 0.195(240) = 46. a a)Worked examples 47 input of Fe with flux input of Fe with dust 0.064215) = 13.76 (0.120(50) = total Fe input to the furnace = 336.56 output of Fe with flue dust = 0.120(60) output of Fe with blister copper = 0.003(247.3) ‘amount of Fe entering the slag = 328.62, Material balance for Zn on a daily basis : input of Zn with copper concentrates input of Zn with slag concentrates input of Zn with dust = 0.220(80) total Zn input to the furnace = 23.4 ‘output of Zn with five dust = 0.220(60) = 13.2 output of Zn with blister copper = 0.001(247.3) = 0.25 i ‘amount of Zn entering the slag = 9.95 Maueria! balance for CaO on a daily basis ? input of CaO with slag concentrates = 0,005(240) = 1.2 input of CaO with flux = 0.054(215) = 11.61 input of CaO with dust = 0.013(50) total CaO input to the furnace = 13.46 A output of CaO with flue dust = 0.013(60) = 0.78 amount of CaO entering the slag = 12.68 0.65 Material balance for Al,Os on a daily basis inputof ALO; with lag concentrates = 0.010(240) input of Al,Os with flux = 0.120(215) input of AIO; with dust total AlOs input to the furnace = 29.0 ‘output of AIO with Bue dust = 0.016(60) amount of ALO, entering the slag = 28.04 Stag consents on dil basi > Cansitvent” tons weigh percent . 50; m2 : : Go ne Le shes mo 3s) a me 500 rE ma 48 2 g98 Lat $ 1% 100 Rea) sk Tol ras 50 0.00 7] Material balance for S on a daily basis (excluding S in the fuel oil) i input ofS with copper concentrates = 0.301(1000) = 301 ; input of S with slag concentrates = 0.068(240) = 16.32 } input of S with Dux = 0.020(215) = 4.3 + input of S with dust = 0.140(50) total input to the furnace = 328.62 ‘output ofS with flue dust = 0.140(60) = 8.4 a4B 2 Material balances in metallurgical processes ‘output of $ with the slag = 0.01(785.9) = 7.86 output of $ with blister copper = 0.015(287.3) = 3.71 amount of § converted to gases = 308.65 fraction of S converted to gases = 308.65/328.62 = 0.9392 2 Material balance for O on a daily basis Because smelting is essentially an oxidizing process, the following simplifications can be made. (1) the species Al,0s, CaO, and SiO, do not undergo any reduction during the process, Therefore, the oxygen associated with them will not be considered in preparing the material balance. (2) Water vapor does not react with any substance during the smelting. Hence the oxygen associated with it will not be included, input of0 from copper concentrates = 0,064(1000) = 64 input of O from slag concentrates = 0.093(240) = 22.32 input of O from ux = 0.0125(215) = 2.69 input of © from dust = 0.091(50) = 4.55 total O input with the charge = 93.56 ‘output of O with flue dust = 0.091(60) = 5.46 output of O with blister copper = 0.006(247.3) = 1.48 output of O with slag total O output net O transfer from air to liquids 8 ‘This constitutes 31.2% of the O in the charge 10 the furnace, exclusive ofthat associated with Al,Os, CaO, SiO2, and H,0. Blast calculations on a daily basis volume of air supplied = (11 x 10*)(24) moisture content = 10 p/m? total pressure = 755 mm temperature = 293°K 6.4 x 10° m Consider 1 m? of wet air at this temperature and pressure. It contains HO, O3, and Na (+ An). Amount of Hi ‘number of gram-moles of H;0 10g 101s = 59 Assuming ideal-gas behavior for water vapor PyoV = moRT, V = 1m! = 1000 liters, T = 293°K, 0.08206 liter-atmig-mole“K Pao = (5!9)(0.08206)(293/1000) = 13.36 x 10° atm = 10.15 mm Po, = 0.21(755 ~ 10.15) = 156.42 mm Py, = 0.78(755 ~ 10.15) = $80.98 mm Pa, = 0.01(755 ~ 10.15) = 7.45 mm ‘no, = (156.427760)(1000)(0,08206 x 293) = 8,560 g-motes ‘x, = (580.98/760)(1000)(0.08206 x 293) = 31.794 g-moles ‘haw = (7.451760)(1000)/(0,08206 X 293) = 0.408 g-mole In the entire volume of air supplied, kilogram-moles of O; = (26.4 x 102)(8.560) = 22,598 kilogram-moles of Nz = (26.4 X 10°)(31.794) = $3,936 ilogram-moles of Ar = (26.4 x 10°(0.408) = 1077