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CHAPTER ONE

MATERIAL BALANCE OF METALLURGICAL SYSTEMS

GROUP 1

1.1 Dimensions and Units


A dimension is something that can be measured or quantified. The best known dimensions are distance related: length, area (length squared), and volume (length cubed). Mass and time are also dimensions; so are more complex variables like viscosity, tensile strength, and electrical resistivity, etc. Dimensions are grouped into two types: simple and derived. Derived dimensions are those that are a function of two or more other dimensions. Velocity, for example, is a unit of length (miles, feet, microns, etc.) divided by a unit of time (minutes, hours, days).
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The concept of a unit is as old as the need of mankind to measure something: e.g. a time interval, the distance a spear could be thrown, the size and weight of a rock, etc. A unit is a standard magnitude of a given dimension against which other magnitudes of that dimension can be compared. The width of this page is equal to seven of a unit of length called an inch; the thickness of this book is equal to a few hundred of a unit called a page.

It is well known that there is more than one available unit for nearly all dimensions; for commonly used dimensions such as weight and length, there are literally dozens of units. Among the reasons for this are the

"popularity" of the particular dimension, the history of a dimension, convenience, and lack of communication. The system used most often are: The English System of Units: this system is based on foot pound - second; therefore, this system is called the FDS system. The French System of Units: this system is based on centimeter-gram-second; therefore, this system is called the CGS system.
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The International System of Units: this system is better known as the SI system; this system is based on meter-kilogram-second.

1.2 Simple Units

1. Amount (numbers), 2. time, 3. length, 4. mass and weight, 5. temperature, 6. electrical charge, and 7. luminas intensity.

1.3 Derived Units


as an example: Energy: the SI units of energy are kg.m2/sec2 which is known as (joule). Pressure: the SI unit of pressure is the Pascal (Pa) which equal (kg/m.sec2). Density: it is defined as the mass per unit volume; thus, the density SI unit is (kg/m3). The specific gravity: it is defined as the ratio between the density of the material to the density of water at 25 C (1000 kg/m3 or 62.4 lb/ft3); thus the specific gravity is a unitless number.
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1.4 Analysis
There are two types of analytical units; those are concentration and composition. Concentration has units similar to density (gm/lit) while composition numbers are unitless composition values; e.g. the

fractions, the percentages, etc. could be on weight base, volume base, mole base, etc.

1.5 Temperature Scales

1.6 Weight Percent and Mole Fraction


To convert from weight percent, Wi, to mole fractions, Xi, we use the formula: Xi= (Wi/Mi)/(Wi/Mi) To convert from mole fractions to weight percent we use the formula: Wi = [(Xi Mi) / (Xi Mi) ]*100 where Mi is the atomic (or molecular) weight of component i.

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1.7 Stoichiometry
Most ionic compounds are stoichiometric compounds, i.e. one gram-mole of these compounds consists of numbers of gram atoms of the elements forming this

compound according to the chemical formula of the compounds; e.g. one gm-mole of CaCO3 consists of one-gm atom of Ca, one gm-atom of C and 3 gm-atoms of oxygen. A discussion of stoichiometry begins with a relatively simple observation about most chemical compounds; namely that the atomic ratios of the elements in them are constant.

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The atomic ratio of calcium to oxygen in calcium oxide is always 1: 1; the atomic ratio of magnesium to silicon in magnesium silicide is always 2:1. Because of this, a gmmole of silicon added to an alloy in the form of magnesium silicide will always bring with it two moles of magnesium; a ton-mole of calcium oxide added to an iron blast furnace in the form of limestone (CaCO3) will always bring with it a ton-mole of carbon dioxide. Such compounds are called stoichiometric, and most ionic compounds are of this type.

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1.8 Balancing Chemical Reaction


The usefulness of compound stoichimetry in making mass balances lies in the fact that a constant atomic ratio implies a constant mass ratio of its elements as well. This principle is the base for balancing the stoichiometric reactions; e.g. by considering the reaction: a Fe3O4 + b CO d FeO+g CO2 The stoichiometry of the different elements shows the following:

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Fe: C: O:

d = 3a b=g 4a + b = d +2g

(1) (2) (3) (4)

Let a=1 then d=3, 4 + b = 3 + 2g

From equations (2) and (4) we can reach to the following: g = 1 and b = 1; now the previous reaction can be written as: Fe3O4 + CO 3 FeO + CO2

1.9 The Stoichiometric Coefficient


The stoichiometric coefficient gives the limiting values for the reagents.

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1.10 Limiting & Excess Reagents


The level of excess reagent required in an actual material-processing is given by: % excess = [(na nR) / nR] x100 where na is the actual mass and nR is the mass required by the reaction. In most cases, an excess of one or more reactants will be deliberately added. There are several reasons for this; those are: 1. it is thermodynamically impossible for a reaction to go to completion unless an excess of one or more reactants is present,

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2. many reactions simply go faster if there is a large excess of one or more reactant, and 3. in solid-state reactors, where getting good mixing can be a problem, adding an excess of one or more compounds can help ensure the reactants stay in contact with each other .

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1.11 Systems and Processes


In order to define a system of substances, a portion of the universe is set aside by creating system boundaries. The form such boundaries take define: open systems, systems. An open system is the one which is capable of exchanging energy and/or mass with its surroundings A closed system is the one which is incapable of exchanging mass with its surroundings but capable of exchanging heat with its closed systems, and isolated

surroundings.
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An isolated system is the one which is incapable of exchanging heat and mass with its surroundings. A process is defined as the physical or chemical action that occurs to the feed in materials transferring it to new forms inside the system. A stream is a material flowing into or out of the process and should be separated from the universe. Each process must has at least one input and one output streams. The location into which the input streams flow and in which they will be treated to

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generate the materials in the output streams is known as the magic box (a reactor). Process streams and the content of the magic box may be characterized as homogenous or heterogeneous. A batch process A semi continuous Steel Converters Blast Furnace

A continuous process Continuous Casting

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1.12 Flow Sheets


What is a flow sheet? A flow sheet is a schematic simple drawing showing the material streams flowing in and out of the units (or reactors) used in a given process to yield finally the required product. A good flow sheet may contain:
1. simple drawing of the process, 2. properties of the process streams, 3. the appropriate input and output locations of streams entering or leaving a unit operation, and 4. the operating characteristics of the unit operations.
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The Total Balance Equation:


Reactor (Accumulation)

feed input streams

output streams

For batch process: mass input = mass output + accumulation In continuous process: ss i ut u it ti e ss ut ut + u it ti e u u ti u it ti e

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1.13 The Number of Degrees of Freedom of a Reactor


The number of degrees of freedom of a reactor in a system for carrying its material balance is given by: F = CS R where: C = number of components, S = number of streams, and R = number of restrictions. The restri ti I. mass s, R, i its re: balance equation for each

component, II. the total mass balance equation for the whole system,
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III. the independent percentage given for each component in each stream, and IV. the atomic ratio in a compound in a reactive system. What does it mean when F has: v ue f zer sitive v ue e u ique v ue, set f e ugh rre t

information, or eg tive v ue values.

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GROUP 2

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1.14 Material Balance of Nonreactive Systems


Mass balance equations are based on the law of conservation of mass not only to the feed streams and throughout streams but also to the weight of each chemical element and constituents . Therefore, the mass balance equation are: feed streams mass = thr ugh ut stre ss f e h e e e t (or chemical compound) in the feed streams = mass of this element (or chemical compound) in the throughout streams
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ss

Choosing a basis: a reference amount of given basis. component should be specified as a

Focus on the consistency with units; i.e., use the same units.

Multiple-mass balance might include: the recycled stream: where fraction of end stream is recycled with the input stream (iron ore sinter), the return stream: when the whole output stream is recycled, the by-pass stream: when fraction or all of the stream by-passed the next unit,

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bleed streams: The stream passes through purification process then returned back to the reactor ( purification of electrolyte ), and purge stream: part of the output stream is purged recycled. out while the remainder is

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1.15 Measures of Performances


1. Recovery: it is the fraction or percentage of a specified component input to a system that winds up a desired process stream. 2. Rejection: it is the fraction or percentage of a specified component input to a system that winds up in the undefined process stream (tailing). 3. Yield: the amount per batch or unit time of some specified output stream divided by the amount of specified input stream. 4. Ultimate yield: yields calculated using system boundaries drawn around an entire process.
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5. Consumption: it is the inverse of yield. 6. The degree of completion. 7. The distribution coefficient. 8. Selectivity separation factor: SF=Mn /mN M and m are the concentrations of the desired component, N and n are those of undesired components. Capital letters indicate the desired product streams and lower letters represent undesired stream. 9. The selectivity index (SI): SI= F /

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1.16 Thermite Welding Process

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This figure illustrates the combustion of aluminum powder mixed with iron oxide in the crucible to produce sufficient heat to melt the iron produced by this reaction: 2Al+Fe2O3 = 2Fe+Al2O3 The molten iron is then poured into the gap between the two pieces of metal to be welded.

1.17 Material Balance of Combustion Processes

Many materials processing operations takes place at room temperature, while other requires the use of high temperatures.
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Generating high temperature requires an amount of energy. One of the most common processes of energy production is the burning of fuel. Both organic and inorganic materials are used as fuels.

1.18 Type of Organic Fuels

1.18.1 Natural Gases


Natural gases are the most commonly used type of gaseous fuel.

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Presence

of

other

compounds

causes

problems because different natural gases will give off differing quantities of heat and offgas per unit volume when burned. So, the amount of air needed to burn a given volume of different natural gases changes with composition. Example: The amount of air required to completely burn one standard cubic meter of Alaskan natural gas (99.6% CH4 and 0.4%N2) at standard state can be get by : (1/22.4)*1000= 44.615 gm-mole A chemical reaction for Alaskan gas can be written as: (a CH4 + b N2 ) + (cO2 + d N2) = e CO2 + f H2O + g N2
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By inspection, a=e and f=2a=89.23, the values of a=44.44 and b=0.18, Knowing e and f sets up an oxygen balance: c= (2e+f) = 88.87 moles O2 This amount of oxygen can be divided by 0.21 to get 423.2 gm-mole of air needed to burn one standard cubic meter of Alaskan natural gas. Converting this to Kg-moles and multiplying by 22.414 m3/Kg mol gives 9.49 m3 for the volume of the required air.

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1.18.2 Fuel Oils


Carbonaceous liquid fuels are better known as fuel oils and they consist of a large number of hydrocarbon compounds. In addition to C and H, most fuel oils contain a little sulfur, which burns to form SO2. Example: fuel oil contains 86.4% C, 11.6% H, and 2.0% S, how many standard cubic feet of offgas will we have to handle when one u.s gallon of this osil with 10% burn excess air? Its specific gravity is 0.910. Since density of water in English units is 62.4 lb/ft3 at room temperate, multiplying this
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value by 0.910 gives a density for the oil of 56.78 lb/ft3. Using conversion constants: thus, the weight of a gallon = 56.78 (lb/ft3) 6.1337 (ft3/gallon) = 7.59 (lb/gallon) i e the fue i t be se r ted i t its

compounds, we will use a materials balance based on its elemental composition. Setting up the equation: (a C + b H + c S ) + (d O2 + e N2 ) = f CO2 + g H2O + h SO2 + j O2 + kN2 multiplying the 7.59 pounds of fuel oil in a gallon which was just calculated by the mass fractions of C, H, and S; and dividing by their atomic mass, yields h=c and
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a = 0.546, b = 0.874, c = 0.00474; and since f=a, 2g=b, and d = f + g + h + j If j = 0, 0.769 lb-moles of O2 are required, multiplying this by 1.1 produces an actual input of d = 0.846 Multiplying (d) by 79/21 results in

e=k=3.183 lb-moles of N2 which gives an actual value of j = 0.077. Adding f, g, h, j, and k determines the total quantity of off - gas produced by burning the fuel oil, 4.248 lb-molls, multiplying this by the 359 standard ft3/lb-mol produce 1525 standard ft3 off-gas per gallon of fuel oil burned.

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1.18.3 Solid Fuels

There are a lot of solid carbonaceous fuels as: wood, charcoal, manure, etc. The Ash: it is the xides th t d t bur r

vaporize when the coal is set on fire such as alumina, hematite, lime, silica, magnesia, etc. Volatile matter: it is the unfixed carbon which is chemically bonded to other elements that tends to form gaseous compounds when the coal is heated in absence of air. Coking: it is the process of driving off the volatile matter in coal by heating in absence of air.
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Example : Calculate: (a) The amount of coke recovered per ton of coal, (b) The volume of dry off - gas produced.

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Answer: Multiplying one ton of coke by 6.7% gives 67 kg of ash, dividing the 67 kg of ash by 0.097 yields 690.7 kg of coke per ton of coal. To get Sulphur in gas = (1000*0.014) (690.7*0.011). Solving this equation produces 6.40 Kg (S) that has to wind up in the off-gas, dividing this number by 32 0.013 yields a total of 15.36 Kg-moles of dry off-gas produced,

multiplying this number by 22.414 produces 344.25 m3 of off-gas at standard state per ton of charged coal.

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1.19 Working Backward


The previous examples had something in common, that the specified inputs to given process determined what came out. I r ti e it s eti es d es t w rk this

way, as limitations on composition or properties of the products will dictate the input. This problem may be solved by choosing the products as basis, so the solution is worked backward.

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In the process of roasting pyrite the input is a concentrate 75 %( FeS2) and 25% Silica and the roosting reaction is: 4 FeS2 +11 O2=2 Fe2O3 +8 SO2 Some of pyrite might react to form ferric sulphate: 2 FeS2 +7 O2=Fe2(SO4)3 + SO2 To keep the volume percentage of SO2 in the off-gas below 6.3%, we must solve the material balance of the reaction: [a FeS2+b SiO2] + [c O2+d N2] = [e Fe2O3 + b SiO2] + [f O2 + d N2 + g SO2] There is no need to use more than one variable for silica and nitrogen. Assume one ton of pyrite concentrate:
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Starting with 6.3 Kg-moles of SO2 in the off gas, so: Fe: a=2e, O: 2c=3e +2f +2g, and S: 2a=g. By using the ratio O2:N2 =21:79, the problem can be solved to obtain the needed air to roast certain amount of pyrite by considering: C/D =79/21 The base equation is: f + d + g=100

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1.20 The Use of Ledger


The following figure is a schematic drawing of the blast furnace for the manufacture of pig iron. As shown in the figure we have four process streams entering the blast furnace ,those are: 1. an ore containing iron oxide, 2. coke, 3. flux (mainly limestone), and 4. blast air.

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Three process streams leaving; those are 1. top gas, 2. slag, and 3. hot metal. Example:

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w we eed t write wh ts g i g i wh ts i g ut s he i re ti :

[hfFe + hsSi + hmMn + haAl + hhH + hoO] + [cc C+ caAl + csSi + cfFe + cuS + coO] + [llCa + lcC + lmMg + lsSi + loO] + [boO + bbH + bnN] = [pfFe + pcC + psSi + pmMn] +
[sfFe + sfCa + ssSi + saAl + suS + smMn + soO] +

[tcC+thH+tnN+toO] Each variable is separately identified with a first letter that defines the particular stream, and a subscripted letter identifying the element.

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It seems to be hard to solve this equation; we need a better system which is the ledger sheet. The ledger sheet for blast furnace operation is shown in the following table:
LEDGER SHEET FOR IRON BLAST FURNACE MASS BALANCE ( Units = Kg-mol per Tonne of Pig Iron) Stream
Ore (h)

Fe
hf cf 0 pf sf 0

Mn Si
hm 0 0 0 pm sm 0 hs ls cs 0 ps ss 0

Al
ha 0 ca 0 0 sG 0

Ca
0 lc 0 0 0 sc 0

Mg S
0 lg 0 0 0 sg 0 0 0 cu 0 0 Sn 0

C
0 lc cc 0 pc 0 tc

H
hh 0 0 bh 0 0 th

O
ho lo co bo 0 so to

N
0 0 0 bn 0 0 tn

Limestone (l) 0 Coke (c) Blast air (b) Pig Iron (p) Slag (s) Top Gas (f)

The rows in the ledger sheet represent various streams, with input streams at the top separated from output streams at the bottom.
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The start will be carried out to obtain the possible values of coefficients at the

horizontal rows then material balance is used for vertical columns to complete the sheet of the process.

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