PART B-PRINCIPLES OF PYROMETALLURGYCHAPTER 3 MATERIAL AND HEAT BALANCE OF PROCESSES ‘The product output of any process depends on the amount of materials consumed. as raw materials and the chemical reactions taking place. Similarly, the energy requirements are related to that required for heating of material to sufficiently high temperatures and sustaining the chemical reactions. Material and heat balance calculations aim at estimating inflow and outflow of mass and energy respectively ‘These are essential plant records and routine calculations for plant operation. Before attempting to calculate the raw material or energy requirements of a process, itis desirable to first obtain a clear picture of the process. The best ‘way to do this is to draw a flow diagram, sometimes also called flowsheet. 34 FLOW DIAGRAMS ‘A flow diagram isa line diagram showing successive steps of a process by indicating the pieces of equipment in which they occur and the material steams centering and leaving each piece of equipment. Flow diagrams are very imporant for saving time and eliminating mistakes. The following guidelines should be observed. 1. The flow diagram should show the unit operationsprocess by simple rectangles. 2, Ina flow diagram each arrow should represent an actual stream of material in a single phase. Thus a gaseous mixture of carbon dioxide, oxygen, cazbon ‘monoxide, nitrogen and water vapour, coming out of a combustion chamber should be shown as a single stream of gas and not as five separate steams. On the other hhand, slag and metal produced by a blast furnace should be shown by two separate streams, the blast furnace itself being indicated by a simple rectangle. ‘A typical flow diagram is shown in Fig. 3.1 The diagram describes extraction of copper from a low grade ore. 32. MATERIAL BALANCE PROCEDURE Material balance is essenslly an aplication ofthe law of conservation of sas. The following equation describes in wor the principe of general material balance applicable wo processes both with and wilhow chemical reactions. Accamtiono man] _ [ln simesh ysen-]_ [Ong toh [Saree] = [Since -[Smatee) on Depending on the magnitudes ofthe last wo terms of Eq. 3.1. the accumulation ‘may be positive or negative. The equation, writen simply as oe ee ARAAARMARAARNMARAR36 Principles of Extractive Metallurgy Composition of maul Ore fre mine = 1 Ca, 38 Fe, 38S Flaaionoooennte = 25% Cs, 25% Fe, 35% S, $8 S10, Tang fo fotion = 01% Ca, 22% Fe, L895 us for meting = 65% Si, 15% FeO Mate = 35% Cu, 35% Fe, 25% § frm mate meng = 05% Cu, 45% FeO, 36% SiO, Shy from converter = 3% Cu, GDR FeO, 25% S10, — (a }+-— 1 Cocentrate Tiling Boosting Je-air Flux m9 oases to waste smelting 4 Slog to woste i Flux ‘ir ——of Converting Gases to waste T » Sag <— Blister copper (99% Cul [Fasting ] (anodes! Tecrenyte ng 995% copper Fg. 3.1 Pow dagen for exrction of coppe rom # lw gree oe accumulation = input ~ output ‘efces furber when tere fo accumulation within dhe system. I that ase oe input = ouput G2) ‘This is applicable to a batch process which involves treatment of a given mass of materials in a process after which the products ae taken out. Material and Heat Balance of Processes 3 If a process is operated such that, overlong periods, continuous steams of ‘materials enter into the processing unit and continuous streams leave the same then itis called a continuous process. In such a process one is concemed with the rate of input and rate of output of materials f une continuous process runs at steady state, then the chemical compositions of the input materials and output ‘materials remain unchanged and there can be no accumulation within the system either. In such a situation, the material balance equation is writen as Rate of input of materials ino the system ‘= Rate of output of materials from the system 63) [In other words, for both batch process and continuous process, what oe ‘come out. Tn processes in which chemical reactions take place resulting in formation, ‘consumption and/or transformation of compounds, one must apply the principles of stoichiometry as well as those of material balance. It should be noted that, ‘material balance holds on the total mass of material but not on moles. Thus while ‘one mole each of hydrogen and chlorine react to give two moles of hydrochloric acid gas, one mole of nitrogen reacts with three moles of hydrogen to produce ‘wo moles of ammonia. One mole of limestone decomposes to produce one mole of carbon dioxide and one mole of CaO. In every case, however, the total mass ‘before and after the reaction remains the same. For material balance, a convenient basis of calculation is to be chosen. In Ccontinvous processes, its ether unit time (an hour in aday) o unit mass of product ‘Gay, one tonne of hot metal forthe blast furnace). For batch processes itis either ‘the entire batch oF unit mass of product. ust 32.1 Stoichiometry Imagine a process shown’ in Fig. 32 and assume it wo be a steady state one. « 2 Fig 32. nena rest A,B,C are rates of input (masstime) of different feed materials and X, ¥, Z are rates of output of different products. Let 1,2, 3,4 ..n denote the various chemical clemenis and a,b, , denote the weight percentages of element in A, B, C. Then the balances of chemical elements yield the following equations: OA +62 4 oC aX -yF 4240 GA + DB + 6C~ 2X -yY- 32 =0 Ga) GA + 6B + 6C-2X~y~ 22 =0.8 Principles of Extractive Metallurgy Also from Eq. 33), +B +C-X-¥-Z=0 es Altogether 6 (n+ 1) quantities are involved in these equations. Only (n + 1) of ‘them can be solved from these (n+ 1) simultaneous equations. The value for others rust be given ‘The preceding equations are based on the law of conservation of mass applied to individual chemical elements. During any chemical and physical processing (other than nuclear reactions), elements are preserved though their states of ‘combination may change. ‘Mathematically the problem appears to be straight forward. However, obtaining accurate solution may be difficult. Also, some errors occur when a quantity is calculated by taking the difference between two large quantities. If some of the {feed andjor product materials are gases then Gas Laws may be employed in order to convert volume percentages into weight percentages. If all the necessary information is not available then appropriate assumption should be made. 322 Steps in Material Balance Calculation ‘The generally recommended procedure for material balance is as follows. (a) Represent each process by a rectangle and indicate each feed or product ‘material by an arrow. Write complete flow diagram. (©) Gather all known data in a table accompanying the sketch or, if there fare not too many data, put the data on the flow diagram itself, (©) Make suitable assumptions if necessary. (@ Choose a convenient basis for calculation, () Write the overall chemical reactions that take place in the process. (0 Write the element balance equations. () Solve the equations. (h) Make up the material balance table (i) Check by an independent method thatthe calculations are correct, Example 3.1 ‘A. ead sinter to be smelted in a blact furnace analyses 8% CaO, 25% and 15% Fe. In smelting this sine, a sag is desired with C20, FeO and SiO, in the proportions. C20 : FeO: SiO, = 4 ‘To obtain this slag, ion ore and limestone of the following analyses ae added to the charge Wit Fe Wi CaO Wi SiO, Iron Ore 450 05 150 Limestone 20 460 80 In addition, coke isto be added to the charge as a fuel in an amount equal to 12 percent of the weight of (simer + iron ore + limestone). The coke contains 25% Fe,0, and 12% SiO,, ‘Assuming that all the lime, iron and silica enter the slag as CaO, FeO and ‘SiO, calculate the weights of iron ore, limestone and coke w be used per metic tonne of lead sinter. Material and Heat Balance of Processes 39 Solution (4) The process of smelting lead sinter is represented by the rectangular block diagram in Fig. Ex. 3.1. All the known data have been shown tere itself, Values to be calculated are also indicated by question marks (W, denotes weight of species i), Coke @i2te(Sinter+0re +Stone), Nee? (25% F203 12%5102) sinwr torre [1208 |e stagtcaos0 viost | siogectthm srce0,2snsionsshFa—At purrs | ton or. re Fe-tS te ,C20°08 ‘ Lmestones i =? (Fe-2%,Ca0-464 $107 ee eee preteens (©) There are several chemical reactions. These have not been identified. Also, fossa e are asereins eet eapeiereeae paceleset cree es ur ateene Se ee ee oe Soe es Ce ym A a eee ered eee ees ev xaoex Bema oo (Fe0 in limestone) (FeO jin slag) 1x 008 + Wy x000S + W,x 086 (CaO in sinter) (C20 in iron ore) (CaO in limestone) A RAHRAAAAAHHAHORAHOMEOOOEEEEe606 555608 40 Principles of Extractive Metallurgy oe xT 32) S10, batance 1x025 + WyxOIS + W.x O12 (SiO, in sinter) (SiO, in ror ore) (SiO, in coke) +Wx008 = wx 33) (Si0, in timestone) __(Si0,in slag) ‘The preceding equations are based on the assumption that all the lime, iron and silica enter the slag phase (©) From overall material balance We= 01114 We +H) 34) ‘There are 4 unknowns, viz. Wo, We, W, and W,. They can be determined by solving the 4 simultaneous equations (Ex. 3.1 —Ex. 3.4) Answer: Wo = 93 kg, Wi = 195 ke, We = 155 kg per tonne of lead sinter. Example 3.2 Steel is being made in an L.D. converter. The metallic charge consists of hot ‘metal and scrap in the rao of 4: 1. The hot metal contains 4% C, 1% Si, 1% ‘Mn, 0.3% P and rest Fe. Oxygen of 99.5% purity is blown for refining. Lime, analysing 2% SiO,,3% MgO and rest CaO is added as fux. The gas leaving the converter has Po/Pco, ratio of 1: 1. 2% of total Fe charged is lost in the slag 1s FeO and Fe,0,, the ratio of ferous to ferric ion in slag being 1 : 1. The steet may be assumed to contain 0.2% C, 0.2% Min and rest Fe. Assime thatthe slag is t0 contain $0% CaO. Also ascume that the efficiency of oxygen utilization is 90%. Calculate the following per tonne stet: (@) Weights of hot metal and scrap to be charged (b) Oxygen to be blown in m? (STP) (©) Weight of lime to te charged (@ Weight of sag profuced. Solution (@) The process of refining ho: mal into ste! is represented by the rectangular block diagram in Fig. Ex.3.2. Allthe known data have been shown there including the assumptions. Values to be calculated are indicated by question mack, () Basis of calculation is 1 tonne of stel (©) Chemical reactions are [si] + 0, @ = Gio) [Mn] + i/2 ©, (g) = (Mino) [Fe] + 12 0, (@) = (FeO) Material and Heat Balance of Processes 41 oxygen( 995 fone Ve, Eticieney «80% Ac ORM oh lization Hot metals eared 21344 MgO, cest CaO) BASIS : | TONNE OF STEEL ig. Bx. 32 Rectangular bok ingram for refiing of bt metal in LD. conver 2 [Fe] + 320, @ = (Fe, 0) {C} +120, @=CO® {(C} + 0, @) =CO, 2 IP +520, (@) = 0) where {] denotes metal phase and ( ) denotes the slag phase. (@) Calculation of weight of hot metal (Wy) and weight of serap (Wc) per tonne of steel: Fe balance yg 1.00 + Wy 0937 vas Fe in scrap Fe in hot metal) (1-002) = 1x 0996 Ge in steel) “The factor (1 ~0.02) takes account of 2% 05s of total Fe into the slg. Again. Wes E36 Combining Eqs. Ex. 35 and Ex. 36 Wy = 0857 tonne = 857 kg and Wye = 0.214 tonne = 214 kg. (©) Calculation of volume of oxygen to be blown per tonne of steel: ‘Table Ex. 3.1 presents te calculations based onthe stoichiometry of chemical reactions noted previously. Si, Ma, C, and P come from the hot metal ony. Since2 Principles of Extractive Metallurgy 254 Che pet ere SO. eras ce ec a cn hee a : scalar efearnnasatac aman comet a WY cuiniencmabe asters aes. ners = 9567 294 5 100, 100 aX 24x pe Xo = 678 wm? (STP) Let might of tine oe cared pe uae of lb Wing No sag contin S08 Cad snd at 80, and Mga ne at eee ‘CaO balance W, x 095 = W, x05 37) where W, is weight of slag in kg. Again, W, = W, + 59.73 x. 38) TABLE Rx. 31 Rests of olchlomett clelations Bonen Weighs ote Newel Weigh of omgar Wel i Loman Weigh of dag ie, tg oxi ead forming onde kg, oS cag SE 1614 co, ‘aoe = st 457 So, 979 " 836 Me ss Mad 1st aa 2st 1, 332 59 Fe 995 236 278 995 Fe, 25 mar tote HAR, Teal 1670 Bm Sn since $9.73 kg of slag forming oxides originate from oxidation Eqs. Ex. 3.7 and Ex. 3.8, we obtain ee W, = 6637 kg W, = 126.7 ke. ‘Answer : Per tonne of steel, (4) Weight of hot metal = 857 kg ‘Weight of scrap charged = 214 kg (©) Total volume of exygen to be blown = 678 m? (STP), (©) Weight of lime to be charged = 66.37 kg (© Weight of slag formed = 126.7 kg Matesil and Heat Balance of Processes 4“ 33 A NOTE IN CHEMICAL ANALYSIS AND SAMPLING ‘Material balance calculations require compositions of some ofthe inputs or ‘ourputs and hence the need of chemical analysis. Moreover, analysis of raw ‘materials, intermediate end final products isa necessity for evaluation and control ‘of product quality, Therefore, plants engaged in extraction and refining of metals usually have extensive analytical facilites. ‘The natural materials as well as industrial products very often contain a significant percentage of moisture. Therefore, the moisture content mast be now For solids, itis determined by measuring the weight loss ofa sample upon drying ‘at 105—120°C. For gases there are various methods. The moisture may be absorbed ina desiccant and weighed. Indirect methods, such as those based on dew points ‘may aso be employed. The moisture conten of gas may be expressed in various ‘ways : percent by volume, gm per cubic meter relative humidity etc, ‘One definite trend in industrial chemical analysis isthe large scale use of| {instrumental methods. This requires more capital outlay no doubt, but is amply rewarded by the speed, labour-saving, and better automation it allows. The instruments are capable of providing inputs directly into the recorders, controller snd computers through proper devices. The high speed of analysis makes the results ‘available 10 the operator while there is still time wo control the process Spectroscopes of various types are the most widely used analytical instruments. ‘A gpical chemical analysis is done ona small sample, which is assumed 19 hhave the same composition as te avcrage of the material in question, How do ‘we make sure that such an assumption is correct? Ths isan important question andall the precautionary measures in sampling ar primarily aimed a satisfying this assumption as best as possible without geting involved in too lengthy a procedure. Since some numerical results ae obtained in good as well as poor samples, the tole of proper sampling is not appreciated by many. However, it goes without saying that poor sampling will give rise to eroneous data and may be quite critical someumes. ome ‘Compositions of materials moving in a process are charactristically non- uniform, except in certain special cases Ths is tue even in continuous processes. ‘The composition may vary with ime or with position or bath For proper sampling, we must have a prior knowledge ofthe extent of variations. ‘The sampling error, ie. the difference in composition between the sample ‘nd the average of the material, is of two kinds: systematic and random, A systematic error arises from the characteristics of the process. Ifa rock consists of two minerals, the more friable one would be found in larger percentage in the lusts and the less friable one would tend to concentrate inthe coarser particles. {In bed of granular solids, the denser and larger particles would tend to go more {o the bottom layers. Ina mine, the composition of the ore changes as we go down Aeeper and deeper from the surface. There are physical and chemical reasons for such systematic variations. The sampler has to be aware of the pattem of variation ‘and only than the error can be minimized. For example, in the first instance cited, he should take samples both from the finer size factions as wel as the coarser size fractions. Jn contrast wo the above, no physical reason canbe atribued to random ero, ARMRARA RAAT ARABRM AAAMAMAMAMMMADRARA44 Principles of Extractive Metallurgy Neither does it show any pattem. Therefore, the only way wo minimize itis have a randomly collected large sample size. Theoretically ifthe entire material is ken asthe sample then there is no error. In terms of stasis, this is equivalent to an infinitely large sample or an infinite number of small sized samples If the ‘number of samples is finite (say m), then an error results, The error, again be predicted with certainty. We can only talk about probable errors. From statistical ‘analysis, it can be concluded that the probable error should decrease by a factor of n'* if we compare the two cases of single and n number of equal sized samples. For granular solids, every particle tends to have a ltl diferent composition ‘8s compared to the others. The probable error decreases if more particles are ‘included in each sample. This means that, fo the same probable error, the sample size shouldbe larger for larger particle size, A typically recommended relationship is M=KDe G6) ‘where M isthe sample mas for the sume probable error, Dis the maximum particle sie, K is an empirical constant, and ‘a’usually lies between 2 and 3. Finally, it should be noted that non-uniformity is usually not much in liquids and gases because of the mixing effects. Non-uniformity tends tobe serious only {for solids, especially in granular solids of natural origin. Even then in liquids where the conversion is taking place fast, as in the L.D, process of steelmaking, ‘considerable composition differences have been found in the liquid bath. 3.4 THEORETICAL BASIS OF HEAT BALANCE, Considerable quantities of heat are required in order to cary out yrometallurgical processes, The cost of energy is always a significant fraction Of the total cost and may even become as high as 304%, A better heat economy, therefore, cuts down the production cost and it can be achieved only if careful bbeat balance is maintained, Just as mass balance isan account of input and output ‘of mass, heat balance is an account of input and output of heat in a process. The effort to cut down the cost of heating has resulted in many new processes. Infact there is a universal move to replace processes which involve frequent int:rmediate hheating and cooling of materials by continuous processes. Continuous casting of ferrous alloys and continuous smelting of copper are exmples of developments in this direction. Such continuous processes eliminate intermediate heating and ‘cooling of materials and reduce requirements of material handling operations and. space. They ar also amenable to beter process contro. The present day techniques ‘of computer simulation and control of pyrometallurgical processes are based on ‘material and heat balance. Other considerations suchas chemical equilibria, reaction rates etc, are incorporated but they are optional depending on their utility. ‘A-complete heat balance for a process lists the contributions of energy from various sources and the consumption of energy by various sinks, i. it lists input and output of energy. Figure 3.3 presents diagramatically the energy balance of 8 typical blast fumace, The same data can also be presented in tabular form, ‘Material and Heat Balance of Processes 45 C+#1/202=C0 283) iSite ct exoyseee ciate fo 00% Heat output (by aitterenced eat opsarbea by Ee) Decorsoation 5 Tech ip ion on | Ssh ig. 3:3 Energy balance for «epi Blast fara 4A. Fist Law of Thermaynamies Jest athe penile of conseration of elanents affords « simple ora approach Sting up mater balance equation the principle ‘coervton fener, sca Fst Law of Thermodynamics ales sun bss or scing upon cegy or heat bale. In both aes, lively Campi accunng cu matron anole of bn got Be sytem cic. remian constant only inthe temperature ranges where there is no change inthe state of aggregation. 2. Changes in heat content due 10 changes in stat of aggregation in pure substances (melting, allotopic transformation and vaporization). These data are also given in the reference books on thermochemical data. Here the changes in heat content are designated as AH, for melting, AV for vapourization ee. 4; Changes in heat content due to chemical reactions inthe system. For these calculations, we proceed from the data on Heats of Formation (A/1) of ‘compounds. This data for common inorganic compounds have been compiled in several monographs and reference books. “The heat of formation of compound AX, ata given emperaure, isthe heat of the following reaction at that temperature, Atk =a Gs) ‘where A and X are the two elements ‘Suppose thatthe real chemical reaction in a sytem is AK + B= BX +A; OH, Gis) where AM, is the heat of reaction. This action can be looked upon as a combination ofthe following two reactions. Aek = AX: AH, (AN) G19) B+ X = BX: AH, (BX) Gan we have, obviously, AH, = BH, (BX) ~ AH, (AX) G8) ‘This isthe Hess? Law ard it allows us to calculate the heat of any reaction from the heats of formation of the compounds involved in it. ‘The heats of reactions depend on the reaction temperature and, therefore, reference books tabulate the heats of formation reactions at various temperate. Even if data are not available atthe required temperature it is possible to easily calculate the value of heat of reaction at an arbitrary temperature T, fom the value of the same available at another temperature 7, by using Kirchof?'s equation whichis writen as (Atle, = Hn + ZH — Hp)paten 2 By Hn) 319) Ikis, however, necessary to have heat conteat data on products and reactants 30 that the socond and third terms of Eq. 3.19 can be evaluated. 4, Change of heat content due to mixing and dilution in solutions. These values are generally not well known and sometimes appropriate assumption is made RRHKRHHHRHARHAEHEE55 53ab000 48 Principles of Extractive Metallurgy ‘regarding their magnitude. Most often they can be ignored altogether because the ‘magnitudes are small Example 33 Calculate the heat of the following reaction per g, mol at 1400 K. 2Zn0%s) + C(s) = Znig) + COCR) Ex. 39) Given : @) Heats of formation (8 H,) of Zn0(@) is = 348,570 Jmol, and of CO (g) is ~ 110/537 J/mot at 296 K. i) Compoundetement Hee Hau 001 Zn0 (9) 36.315 2n(g) 153,454 COW) 35,085 co) 20,642 ‘According to Hest Law, ie. Eq, 3.18 AH, for reaction Ex, 39 = All,(CO) - AH, (220) = 238,033 mol & 298 K, According o the Kirchhof?'s equation, ie. Ea. 3.19 CAH. = BH Daa + Een ~ HDi ~ Elo ~ Hse = 738,033 + 153.454 + 35,045 ~ (56,315 + 20,642) = 249,575 Jimol (Answer) 35 PROCEDURE FOR HEAT BALANCE, ‘The reference or basis temperature with respect to which the heat contents (Gensible heats) of the materials are measured, has to be selected frst. AS stated in the previous section, 298 K is the universal reference. However, we have to fix the reference sate as well. The reference state of a substance is usually taken asits stables state of aggregation (slid, liquid or ga) atthe reference temperature. However, there is nothing wrong in taking a metastable state as the reference one. ‘The basic equation is Heat input = Heat output + Heat accumulation G20, For many processes, the accumulation term is negligible. Hence we may simply Heat input = Heat output @2n This equation is appropriate for a batch process. For continuous processes, the equation will be Rate of heat input = Rate of heat output 622) Again, “Meterial and Heat Balance of Processes 49 Sense heat (beat contents) of ap materi (cluding AM fer changes in the ses of egregain) + Heat evolved ie Sothemicrescns (measured atte reference lemprature and Sina) Heat soplet from ouside be sysem 23) t= Sensible heats of ouput materi (nclting A for change are in the states of aggregation) + heat absorbed in endothermic Toco (meaued athe reference tempat and Sate) yet absorbed in binging input matrl to the referec Tanne dr at oe sea “This equation is consistent with the First Law of Thermodynamics, this is furthes illustrated in Fig. 3.4, Heat input = Tet males Tat paae ‘gengined Hy coming outa Hy Exothermic rections, & Mt sose Tempercture tf Endatherme reactions, 8 Ry coia noterale (Getow reference temperate) gong isp i. 34 Heat balance fo # consant pressure process ‘STATEMENT OF FIRST LAW OF TIERMODYNAMICS : Spgqay,= Op - "= 8H, + Aly + Bg, + ly + ABy Heat Balance input oureur 4 SENSIBLE HEATS OF OUT: 1, SENSIBLE HEATS OF INPUT a PUT MATERIALS, ly MATERIALS, a, 2. HEATS EVOLVED IY XO. 5. HEATS ABsonaeD (ETON. ENOTIERGe THERMIC REX REACTIONS, Airy 1 SUPPLIED ELECTR 6 fears aasona my * Gail. BRINGING INPUT MATERIALS TO REFERNCE TEMPERATURE, Of 17. HEAT LOSS TO SURROUNDINGS. - 80, TOTAL Alf - Aig -W"= Aly + Ay + Bly = 8050 Principles of Exractve Metallurgy For actual eat balance calculation, the following well defined steps should be followed. ‘Step 1 : Work out the complete material balance, Step 2: Select the reference temperature and reference states. Step 3 : Write the process equation and the chemical reactions. ‘Step 4 : Perform the energy balance, calculating TH. and Spy fr the Jefe and right sides, respectively, of the process equation and 7) values for the chemical reactions. Step 5 + Pesform all additional calculations called for. Table 3.1 shows the heat balance for a typical open-hearth process of steelmaking. These data as well as those shown in Fig. 33 indicate the way heat {is contributed and consumed in two industrially important processes. ‘TABLE 24 Typ heat balance ofthe open earth proceso tecimaking eat inp Gea eo, Heat cup Glew db in promt ‘toramed), percent Seoile hea of gu 1410 Hew cman ol ane ge Chemical combined Heat contot of tee teat of te aa 6130 Het ccmtnt of sg Heat ofthe pg ce $50 Refucton of irom oie Heat of air for combusion = O2—_—Redaionof ungunete exes eat content oom, Redacon of rules Times, mp Heat ones fy ifeence) ritaton of (51 Onion of (F ‘Onin of 1) (xdaton of (Mo) (nation of (Fl Oudaion of 15) = as = 10006 Example 34 ‘An open-hearth stelmaking furnace uses a fuel gas consisting of 30% Hy, 18% CO, 17% CH,, 29% N, and 6% CO, for heating. The primary combustion air is preheated to 1000° C: The leakage of cold air through openings may be assumed to be 20% of primary aif. The flue gas contains 30% O,. The temperature of processing of molten stect is 1600°C. Calculate : (a) Theoretical air () Excess sir (in %) (© Adiabatic flame temperature @ Gross available heat Sotution : ‘Material Balance () Basis of calculation : 100 mols of fuel gas; assumption for material balance is that air contains 21% O, and 79% N, by volume. ‘Material and Heat Balance of Processes SI contusion oes is sown byte renga ck diagram a Fi © Be SE vanaf own das tn tsps tines ander of Rls The quomon mars dene he ques 0 be eae. (o ine contin elon ase indeed in Tate Ex 34 @), Siamese ‘auton a have brn preset i (o Trae ren. of mol of orp esind eral 32° = 58x FP = 276 mols ( Cateulaton of excess air, al air et: Lat N, be the oa no. of mos of ooSiitne Molar bane f fae gs (per 100s ft is iy. = 134 + no, of mols of nitrogen in theoretical air + excess air = 134 + 100 (216 - $8) + 003 x FX My Ex. 3.1) since the fuel gas contains 3% O,. ; Solving Eq. (Ex. 3.10), n= 410-7 mols and it contains: 64 mols H,O, 41 mols CO, 123 mols 0,, 2934 mols N;- Excess air = 58.7 mols Excess air “Theoretical air ‘Total air = 276 + $8.7 = 334.7 inols Excess air (in %) = X 100 = 213.% 1 Primary combustion air = 334.7 x qh = 278.9 mols. Heat Balance (© Reference temperature = 298 K, reference state for H,0 is liquid, basis = 100 mols of fuel gas. (@ Assumptions are that the fuel gas as well as leakage ai enter the furnace at 298 K. Fuel gas.nz100mates [Combustion Pm Flue ges,ngs? ‘ chamber ot | (a14zyrest C02, 29% Ng ond ON Furnace | a0 and Ne) Brcop) ot 298% Primary combustion ot, Leakage 0,02na (21% 0347 (2002.79 742 ‘at 298 213 Fi x. 3.4 Recungla block diagram for cmbunion of ful nthe cpen-beath teeming mace PRRRAHSHAHRHARHHALAHAARRAAAHLEERSS | 966666666 8 Principles of Extractive Metallurgy ‘TABLE Ex. 34 (4) Stlclometrccalcnations for combustion reactions ‘Teoria ao. No.of mols of No.of male afmols ot proc in lar Species Comborion reasiont in fuel at oxygtn mgeied ur Barbone » 7 » >. ceh arco, u : Stas n a treo uae co + 6 - pro , ae 3 3 doo 3 z 3 Tal ve w 7m (h) Heat balance : From Eqs. 323 and 3.24, the heat balance equation can be waitten as: Sensible heat of fuel gas ( AH) + sensible heat of leakage air (AH) + sensible heat of preheated primary air ( AH) + heat evolved in combustion reactions at 298 K (A Hr) = sensible heat of flve gas at adiabatic Name temperature aT (AP) (Ex. 3.11) This follows from the definition of adiabatic ame temperature, which is ‘obtained if there is no heat loss from the flame, i. if the combustion takes place adiabatically From assumptions made in (g) above, ‘Alfy= 0 and #1 0. For calculation of other heat effects, heats of formation (AH) ( Cateaation of AHay Bay * (ho i SEY At) (AP ~ Hag) Op hg, ima sit) (Hy ~ Hg (Ex. 3.12) Now om () ste, no, = 2709 x Bb = 58 mols wen29 Es Li mts Ain tom Tite 34 0), (Fins ~ Hyg) per mole O, = (Hyg ~ Hay) per mole N, = 30.5 kJ w ‘Therefore, Alf = 58.6 x 32 + 2203 x 30.5 = 8,594 KI ec “Material and Heat Balance of Processes 3 (@ Calculation of AFey: From data in Table Ex. 3.4 (0), we obtain at 298 K: H, () + $0, @) =H, O (); AH = 286 iS mot" CO ) +10, = CO, ig: A = 283 11 mol! CH, (@) + 20, (@) = CO, (@ + 28,0 0); AH = 891.5 85 mot* ‘Mig = 786 x no, of mols of H, + 283 x no, of mols CO + 891.5 x no, of mols of CH, in fuel gas Ex. 3.13) "TABLE Ex. 34 (9) Value of heat contnts and nts ffrmation® Teclge eto oP serie veaie! all, Taat, Specs = x ext eNO xa mix ry ia cH = = = ons 8 -ns 26 <2 ts oo, aan 20 Tis 3m % 03 mo -ao x 73 aa ° Toms CX Wick mat Blac: Temata proper of clement their oie, aide, abies sd ities, Buln 605, US. Buran of Mines, Washington D.C, USA, 1969) = 286 x 30 + 283% 18 + 891.5 x 17 = 28830 & Caleuation of AH, Hy = En, (Hy ~ Hyg), = T Eng, + PEnp,+ Eig, + PAA Ex 3.14) ‘where the summation is to be done for all the fue gas constituents. We note from () that in fue 4A | Mag = 64, Neg, = 4, Mg = 12.3, My, = 2934, Values of 4a, b, ¢, and d for various species are listed in Table Ex. 34 (b). Caleulations performed at different values of T are presented in Table Ex. 34 (€). TABLE Ex. 3.4 (0) Caleulatlon of (iy ~My) (al values in Jules) ad tLe P32, Xan Le Hylan maw ae = 38 asm S212 0 31368 maze 6282 8 Sat mans 7387 9 Sas“ Principles of Extractive Metallurgy (2) Calculation of adiabatic Name temperature: From the heat balance, ie. Eq. Ex. 3.11, and values of lfgy My, and AU, calulated in (), () and) above, Ally =SHg+ Oy = 859 + 28830 = 37424 Ex. 315) Graphical solution based on Table Ex. 34 (c) yields a value of T= 2443 K = 2170°C. (a) Calculation of Gross Available Heat (GAH): By definition, GAH = Sensible heat contained in five gas at adiabatic Name temperature — sensible heat contained in flue gas at critical process temperature (Ex. 3.16) Here the critical process temperature isthe temperature at which stoc is being processed, ie. 1600°C (1873 K) Hence, GAH = (Ay) suse ~ (4) srs = 3744 - 77,503 = 9921 KI per 100 mole of fuel gas. Answer (@) Theoretical air = 276 mols per 100 mols of fuel gas. (©) Excess air = 21.3% of theoretical air (© Adiabatic flame temperature = 2170°C (@) Gross available neat = 9,921 13 per 100 mol of fuel gas. Problems 3.1 A mixture of Chalcopyrite CuFeS,, Pyrite (FeS,), and Chalcocite (Cu,S) analyzes 30% Cu, 30% Fe and 40% $. Calculate the mineralogical analysis. 3.2 100 tonnes ofa flotation concentrate is roasted per day continuously with dry air. The concentrate contains 75% ZnS, S% PbS, 5% FeS, and the rest inert ‘gangue materials. Assume that roasting converts the ZnS wo ZnO, PbS to PbO and FeS, to FeS,O, and all the sulphur of the sulphides form gaseous SO, and 80, The gases leaving the system analyze 6% SO, and 2% SO,, Calculate (8) rate of blowing of air (Nm°. s"), (b) the excess air, as percent of the quantity theoretically required forthe reactions, (c) the complete analysis of the gases ieaving, the roaster and (d) the quantity of K,SO, which can be manufactured from the sulphur in the exit gas in ¢ day" 33 A basic open-hearth furnace treats a charge composed of the following. Charge Quantity, ¢ Chemical analysis, % Hot metal 120 C-4, $1.05, Mn-1.0, P-03 Scrap 8 C011, Si-005, Mn-0.5, P-003 Ore 6 Fe0s-90, Si0,-5, ALO,-5 Limestone 2 CaCO,-95, SiO ‘Composition ofthe steel tapped from the furnace is: C-0.1%, Mn - 0.2% P-0.03% The slag contains 50% CaO, 15% iron oxide (repored as FeO), and 4.5% MgO, rest SiO,, MnO and Al,O, , P,0,. The furnace is lined with burnt dolomite. Calculate (a) the weight of slag made, () Material and Heat Balance of Processes 35 ‘weights CaO and MgO picked up by the stg from the dolomite lining, (c) weight of stcel made and (d) percent SiO,, MnO and P,0, in slag ‘Assume single slag practice, 3.4 Acopper converter blows copper mate into blister copper. Te following dota are provided. Chemical analysis, % Matte charged CuO, rest Fe and'S Flux charged Si0,80, Cu,S-4, FeS-16 Slag produced $i0,30, Fe0-70 Blister produced Cu-985 The weight of mate charged is 50 t Rate of blowing of air is 3 Nas! Assuming that both matte and fx are charged atthe beginning, calculate (a) weight cof flux charged, (b) weight of slag produced, (c) weight of blister produced, (@ lowing time forthe rst sage and (c) blowing time forthe second stage. 3.5 A Parkes desilverizing ket receives a charge of 40 tonnes of softened lead containing 8.5 kg of silver per tonne. The ist zine erustis formed by adding unsaturated inc crst fom treatment ofa previous charge. This unsaturated crust carries 1.2 kg Ag per tonne and 70% Pb, the balance being Zn. This addition is enough to give 1 kg of Zn per 05 kg of Ag in the kettle ‘The lead takes up in solution 0.52% of its weight of zinc; the rest ofthe ine forms the compound Ag,20, which is removed in a erst containing 70% Pb, Pure Zn is now added in an amount sufficient to remove all the remainin ‘AB 35 AgZn, along with some Pb. Calculate (a) the weight of unsaturated crit to be added first, (2) the weight ofthe first crust removed and (c) the weight of pure zinc to be added. 36 A blast furnace makes pig iron containing : 3.6% C, 1.4% Si, and 95% Fe, The ov is 80% Fe,0,, 12% Si0,, 8% Al,O,. The coke (1 kg per kg of pig iron) caries 10% SiO,, 90% C. The flux (04 kg per kg of pig iron) is pare CaCO, The blast furnace gas has 28% CO and 12% CO, Calculate: Per tonne of pig iron made, (The weight of oe used. i) The weight of slag made. (ii) The volume ofthe blast-furnace gas. 3.7 Pure alumina for aluminium production is produced by the Bayer proces, using Bauxite of the following composition: Al,O, ~ 589%, Fe,0, ~ 6%, SiO, 4%, TiO, ~ 2%, H,O - 30%. The ore is dired, ground and digested with NaOH forming a solution of NaAIO,, The red mud filtered from this solution carries 26% Fe,0,, 21% FeO, and 14% Na,O. Assume that it contains all the FeO, and SiO, that were in the Bauxite and that the SiO, is present in the form of the insoluble compound ALO, Na,O. 3SiO,, 9H. itis desired to have the filtered solution contain 1.5 mol of Ni,O to 1 mole of Al,O,, Calculate (a) the weight of red mud for each 1,000 kg of original Bauxite, (©) the weight of Al,0, lost in the insoluble compound, per kg of SiO,, and Percentage this represents ofthe AO, content of the Bauxite () the total loss ‘of ALO, content ofthe Bauxite, (f) the weight of NaOH used in forming the insoluble compound per kg of SiO, and the total loss of NaOH represented 2 O% PO RPRARARARAA ALAA AAR AAOR56 Principles of Extractive Metallurgy by the Na,O in the red mud and (2) the weight of NaOH used in the process per 1,000 kg of Bauxite, and the percentage of it lost in the red mud, 38 Iron ore, limestone and coke of the following analysis given below are to be charged into an iron blast furnace: Material Chemical analysis, % Iron ore Fe-50, Si0,8, AI,O, ~ 3, H,O-10, Mn-2, and P-0.05 Limestone Si0,-4, CeO- 50, MgO-2, AL,O,-1, H,0-1 Coke Fe-1, Si0,-5, Al,O,-3, H,0-2, C-86, S-1. “The feumance is operated to produce pig iron analyzing 94% Fe, 4% C and 1% Si witha slag basicity (CaO/SiO,) of 1.6. Previous experience indicates that the coke consumption will be 900 kg per tonne of pig iron produced and thatthe quantity of ai in the blast will be 80% of that theoretically required to burn the C in coke to CO. Calculate (a) the weight of ore and limestone to be charged per tonne of pig iron, () the volume of dy air to be blown in Ni? s fora furnace producing 1000 t pig izon per day. 3.9 Find the heat of reaction of the following at 1200 K. 250 (3) + C (graphite) = Za(g) + CO (g) Given the following data (in J mot or J mot K-) ‘AH, (2x0) at 298 K = ~ 348,36 % 10° ‘Hf, (CO) at 298 K = ~ 11054 x 10° G, (@2n0) = 49.03 + 5.11 x 109 T ~ 9.3 x 108 T? (graphite) = 1687 + 4.77 x 102 T — 8.54 x 1087? F (CO) = 2843 + 4.1 x 109 T ~ 046 x 10° (Za) = 22.40 + 10.05-x 10° T, 298 - 692K (aah) = 31.40, 692 ~ 1180 K Zn) = 2081, 1180 K 3.10 Calculate the adiabatic flame temperature of combustion of a bas fumace 425 analyzing 25% CO, 12.5% CO, and rest N, by volume, Theoretical amount of air is being used. Given C, (CO, : 44.17 + 9.04 x 109 TJ mol! K2 G, (Ny : 2789 + 427 x 109 TJ mol? K alt, (CO,) a 298 K: ~ 393.79 KJ mot ‘Other heat data are to be found in Prob. 3. 3.11 A fuel gas, consisting of CO and H, is being manufactured continuously by passing a mixture of oxygen and steam through a reactor containing a fluidized bed of coke, which may be assumed to be pure carbon. The coke and oxygen are fed at 298 K and the steam (at around atmospheric pressure) at 400 K. The temperature insite the reactor is being maintained at 1300 K by controling. the steam/onygen ratio. The fuel gas also leaves the reactor at 1300 K. Assuming that 10% of heat input gets lost by conduction through the reactor wall, calculate (@) the weight rato of steam to oxygen for operation under the conditions described and (b) the chemical analysis ofthe fuel gas. Material and Heat Balance of Processes 2 Given (in J mot’): AH, (H,O) at 298 K = ~ 286.08 x 10° H, ~ Hyg (O,) = 29.98 T + 2.09 x 10? T? + 167 x 10° T* = 9688 Hy ~ Hayl H,O(0) = 75.53 T 225 x 10 298-373 K) H,~ Hag( F401) = 3057 T ~ 5.15 x 107 — 9571 Hy— Hyg) = 27307 + 1.63% 10° T2050 x 1O°T 2114 ‘Other heat data are wo be found from Probs. 39 and 3.10 3.12 A copper converter is charged with 35 tonnes of mat, 10 tomes of flux and makes 21.4 tomes slag. With the help of the following dat, prepare a heat balance ofthe converter at ube end ofthe slagging period and at the end of the blow, Data : Go gat (Maal Chemin ly, pong °C Tek Je C86, F164, $3% = = _ sb.cin (Fen fa, nt at Mae 1000 58 oss Slag 20 1s 104s Ble Cogyer case, 505% ro 8 ows (Gi) Slagging period = 231 min; blister forming period = 110 min; total amount of air blast = 2.47 x 10 4 Nm?, Air is enriched with O,, and it contains 31% 0. (Gi) Mate introduced at 1050°C flux at 25°C and blast at 25°C. (Gv) Heats of formation data: ‘AH for formation of slag from constituent oxides at 298 K is 1580 Joules of SiO, (#) BH at 298 K in KI mot” of the following reactions are: FeS+320, =FO+S0; - 4690 2Cu+0, = 2Cu0; ~ 3207 Cus +2Cv,0 =6Cu+S0; +120 (vi) During blow, temperature of matte, slag and product gases are at 1300°C. (ii) Other heat data are in the previous problems. 3.13 A continuous smelting furnace is heated with water gas 20% CO. SO% H,, Fuel an air enter at 25°C Excess ar is 20% of theoretical air. The operation proceeds satisfactorily and atthe desired rate with the temperature ofthe fuel gases Jeaving the forace at 1200%C. What would be the percentage increase in fuela 58 Principles of Extractive Metallurgy ‘consumption ifthe excess air were increased 10 50% of the theoretical ir? All necessary heat data have already been provided in the previous problems. General Reading 1. A. Bo, Maar Probie McG New Yo 190) 2 Ro. Pin, Unt Paces nBxrscte Mtr, meee aig Coe ‘New York (1973) Ch, 8. ™ 3. Ae. X Stet iy Li Maal and Energy Balas Fei al i gwd Cliffe, New Jersey (1962) mi 4. DM, imma Base Pints ad Catan in Chm Engng, Sere Pence Hal in, Enhwtne Ci New ony (36 Oe 4 Bee Andon nd Lamar A. Wenz route o Caml Pailcerig, McGre Fill Bot Colne, New Ya (at) Ces 6 R Stn, Metal Empnring Vo. 1 gawrig Praca, Addin We Publishing Co. Ine, Load. (1952) Ch3. es 7 ° (CHAPTER 4 THERMODYNAMICS OF METALLURGICAL REACTIONS (Chemical thermodynamics is employed to predict whether achemical reaction is feasible or not, It also allows quantitative calculation ofthe state of equilibrium ff a system in terms of composition, pressure and temperature, Laws of thermodynamics are exact and, therefore, calculations based on thcm arc, in principle, sound and reliable inthis chapter we wll eal mainly with application of thermodynamics tohigh ‘temperature reactions encountered in pyrometalurgy. It will be assumed thatthe reader has some previous exposure to fundamentals of chemical thermodynamics. 4.1 THERMODYNAMIC EQUILIBRIUM [A discussion of reaction equilibria requires precise definitions of some terms. Por example, a system is defined as any portion of the Universe selected for consideration, Rest ofthe Universe outside the system is known as surroundings, ‘The state ofa system is defined at any instant by giving al its state properties such astemperature, pressure, volume, surface tension, viscosity ete. A complete listing of all the properties of a sate is superfluous because many of them are often ‘mutually interdependent Pressure (P), volume (V), and temperature (T) are the most common state variables. When a stale is described by such variables then certain assumptions are made implicitly or explicitly. For example, if here is no mention of magnetic field intensity then it implies that magnetic work is insignificant. Similarly, if surface tension forces are ignored then there is the underlying assumption that surface ‘energy isnegligible. Again P, Vand are interrelated. For example, foranieal gas PV=nRT ay ‘where is he numberof mols occupying volume V.n general, fora thermodynamic substance, lt Vi 42) where the R.H.S, denotes some appropriate function of P and 7. Therefore the state of a thermodynamic substance can be defined by any two of the above three variables provided the only work is that done against pressure. Itshould be noted that amosngst these variables, Vis aproperty which depends ‘on the amount of substance under question. On the other hand, P and T are not ‘dependent on mass. A property such as volume, which depends on the amount of ¢ € € € € € € t € € € € € ¢ € € € € © € ‘ € t