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    Calcination Roasting PredominaceArea

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    Vikramaditya Mathkar
    The document discusses extraction of metals through various metallurgical processes including pyrometallurgy, hydrometallurgy, and electrometallurgy. It focuses on pyrometallurgy, explaining that it is often cheaper than electrometallurgy and hydrometallurgy. Pyrometallurgy takes advantage of higher temperatures to facilitate chemical reactions and the separation of products. Specific pyrometallurgical steps discussed include calcination, roasting, and smelting. Details are provided on gas producers, stoichiometric calculations, heat balances, and predominance area diagrams used in pyrometallurgical processes.

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    Calcination Roasting PredominaceArea

    Uploaded by

    Vikramaditya Mathkar
    226 views48 pages
    The document discusses extraction of metals through various metallurgical processes including pyrometallurgy, hydrometallurgy, and electrometallurgy. It focuses on pyrometallurgy, explaining that it is often cheaper than electrometallurgy and hydrometallurgy. Pyrometallurgy takes advantage of higher temperatures to facilitate chemical reactions and the separation of products. Specific pyrometallurgical steps discussed include calcination, roasting, and smelting. Details are provided on gas producers, stoichiometric calculations, heat balances, and predominance area diagrams used in pyrometallurgical processes.

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    Extractive Metallurgy - Predominance area concepts

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    The document discusses extraction of metals through various metallurgical processes including pyrometallurgy, hydrometallurgy, and electrometallurgy. It focuses on pyrometallurgy, explaining that it is often cheaper than electrometallurgy and hydrometallurgy. Pyrometallurgy takes advantage of higher temperatures to facilitate chemical reactions and the separation of products. Specific pyrometallurgical steps discussed include calcination, roasting, and smelting. Details are provided on gas producers, stoichiometric calculations, heat balances, and predominance area diagrams used in pyrometallurgical processes.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    226 views48 pages

    Calcination Roasting PredominaceArea

    Uploaded by

    Vikramaditya Mathkar
    The document discusses extraction of metals through various metallurgical processes including pyrometallurgy, hydrometallurgy, and electrometallurgy. It focuses on pyrometallurgy, explaining that it is often cheaper than electrometallurgy and hydrometallurgy. Pyrometallurgy takes advantage of higher temperatures to facilitate chemical reactions and the separation of products. Specific pyrometallurgical steps discussed include calcination, roasting, and smelting. Details are provided on gas producers, stoichiometric calculations, heat balances, and predominance area diagrams used in pyrometallurgical processes.

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 48

    Extraction of metals

    Mining Beneficiation (mineral processing) Smelting (extraction of metals) Refining


    Pyrometallurgy Hydrometallurgy Electrometallurgy

    Why pyro metallurgy


    In many cases pyro is cheaper than electro and hydro Employs inexpensive reducing agents Higher temperatures lower the activation energy barrier which opposes the progress of chemical reaction Rate of reactions almost double for every 10C increase in temperature

    Why pyro metallurgy


    Take advantage of the ability to shift the reaction equilibrium with temperature ZnO + C = Zn + CO (equilibrium is at left at 25C. Shifts right at 1200C) M+2I2 MI4 Forward at 200C, reverse at 1400C Physical separation facilitated when products are in liquid or gaseous state
    (eg. Metal + slag ) or volatile chlorides

    Uses lesser space (higher/volume productivity)

    Pyrometallurgical steps
    Calcination ..Remove volatiles, decompose. Roasting Chemical conversion of ore (O2,Cl2) Smelting Reduction of ore (C, H2, electric) Calcination:
    CaCO3 = CaO +CO2 (DGT = 42300-37.7T) ..1000C Product may be leached (water/Acid/Alkali)

    Roasting(Oxidising, Volatilizing, chloridizing)


    ZnS+1.5O2=ZnO+SO2 , 2NaCl+MS+2O2=Na2SO4+MCl2 4NaCl+2MO+S2+3O2 = 2Na2SO4+2MCl2

    Fuel and Ore Preparation


    Coal coke Oil and Gas nH/nC ratio varies from less than 1 to 4 Net calorific value by Dulongs formula Coking (coking coals, low temp, high temp)
    Expels CO2, H2O, C2H6, H2S, H2, NH3..)

    Gasification of Coal (Gas producers)

    DG of some Carbon compounds

    Gas producers
    Gasification of coke and coal Partial combustion with air, O2, steam or CO2. C + O2 = CO2 DG1 = -394100 0.8T J (Dominates at low temp. and high O2) 2C + O2 = 2CO DG2 = -223400 175.3T J Boudouard reaction CO2 + C = 2CO DG3 = +170700 174.5T J With steam H2O + C = H2 + CO DG4 = +134700 142.5T J
    (All DG values refer to graphite as standard state)

    Gas producers
    Coal or coke
    Air only Air+ Steam

    H2O + C = H2 + CO

    Gas out

    N2

    CO2 +C= 2CO C + O2 = CO2

    AIR + STEAM

    Height above grate

    Gas producers
    Role of steam Steam converts physical enthalpy to chemical enthalpy Increasing steam lowers temperature below the required value Alternate operation of gas producer
    Air blown Steam blown (CO+H2, water gas)

    Alternate methods (preheat air, O2+H20, Electric)

    Stoichiometry in gas producers


    Stoichiometric calculations based on reactions between C, H2 and O2 provide
    Relative quantities of reactants used up Quantity of products obtained Composition of products

    Stoichiometry in gas producers


    Calculation procedure Choose the following reaction (shifted to the right at 1000C) 2C + O2 = 2CO Choose the basis (1 mole, kg or tonne) Calculate moles of reactants in chosen basis Calculate moles of other reactants and products (N2?) Convert number of moles in suitable units (wt/vol) Calculate the composition of product in suitable units

    Stoichiometry in gas producers


    Case: Reaction between carbon and O2 + steam. If the mixture has the mole ratio of nO2/nH2O = m, 2mC + mO2 = 2mCO . (if nH2O = 1, then nO2 = m) C + H2O = CO + H2 Which means Reactants Products C = 2m+1 moles CO = 2m+1 moles O2 = m moles H2 = 1 mole H2O = 1 mole N2 (if O2 is from air) (Also consider N2, if O2 is from air)

    Stoichiometry calculations
    Case: Reactions in a mixture of H2O & CO in the temperature range 500-800C.(Assume equilibrium)
    Chemical reaction K @ 500C K @ 800C

    CO + H2O = CO2 + H2
    CO + 3H2 = CH4 + H2O
    n0CO n0H2O

    K1=5.8
    K2=100

    K1=1.2
    K2=0.01
    nH2O nCO nCO2 nH2 nCH4

    tC , Ptot (atm) in presence of catalyst

    Stoichiometry in gas producers


    Assume: n0CO and n0H2O moles of CO & H2O enter the reactor

    Effluent contains ni moles of CO, CO2, H2O, H2 and CH4 Mass balance from stoichiometery nCO = n0CO x - y WherenCO2 = x x and y = moles of CO2 nH2O = nH2O x + y and CH4 respectively nH2 = x + y formed during reaction nCH4 = y ntot = n0CO + nH2O - 2y

    Stoichiometry in gas producers


    ntot = total number of moles ptot = Total pressure CO + H2O = CO2 + H2 Then pi = ni .(ptot/ntot) CO + 3H = CH + H O
    2 4 2

    Then and

    Calcination and drying


    Drying H2O(l) = H2O(g) DH0 = 43.9kJ Calcination CaCO3 900 C CaO + CO2 DH0 = 177.8kJ MgCO3 417 C MgO + CO2 FeCO3 400 C FeO + CO2 200 C Fe(OH)2 FeO + H2O

    Calcination and drying


    CaCO3 + coke Gas
    Preheating zone
    340C

    Solid

    Gas
    800C 900C 1000C

    2
    3
    Air

    Reaction zone
    500C

    Cooling zone

    Air

    Solid

    CaO

    100C

    Heat balance calculations in tutorial

    Heat balance for shaft furnace


    Preheating zone
    Solids preheated to 800C in counter curret by hot furnace gases. No calcination. No combustion.

    Reduction Zone
    Coke burning and CaCO3 decomposition takes place. Avg 1000C. Gasses leave at 900C.

    Cooling Zone
    Burnt line is cooled in counter current with cold air. Burnt lime is cooled to 100C

    Heat balance for shaft furnace


    Calculations
    Assumptions (deviations can be easily corrected for) Excess air used to assure complete consumption (say 25%) Limestone contains 100% CaCO3 (no impurities) Coke contains 100% carbon (no impurities) Disregard heat losses from walls At room temp. assume rO2 = rN2 = rAir Calculate amount of Carbon required to calcine per unit weight of CaCO3

    Heat balance for shaft furnace


    Calculations
    Heat requirement per mole of CaCO3 Reaction : CaCO3(800C) = CaO(1000C) + CO2(900C)
    Input kcal Output kcal

    CaCO3 Heat balance

    Sum

    20.8 CaO 43.8 CO2 CaCO3=CaO + CO2 64.6 Sum

    12.0 10.1 42.5


    64.6

    Heat balance for shaft furnace


    Calculations
    Heat available per mole of Carbon Reaction : C (800C) +(1.25O2 + 4.7N2)(500C) = (CO2+ 0.25O2+ 4.7N2)(900C) .1.25 *(79/21)= 4.7
    Input kcal Output kcal

    C 1.25O2 ** 4.7N2 C+O2 = CO2 Sum

    3.2 4.4 15.5 97.0 120.1

    CO2 0.25O2 4.7N2 Available heat Sum

    10.1 1.7 30.0 78.3 120.1

    ** Combustion air preheated to 500C

    Heat balance for shaft furnace


    Calculations
    Combustion air temperature may be calculated from heat balance of the cooling zone. Calculations show that Carbon required per mole of Calcium carbonate is 43.8/78.3 = 0.56 mole. Theoretical requirement = 0.067kg of C per kg CaCO3 Add 0.1kg to cover heat losses through walls. Find heat surplus which goes out as top gas temp. Compute heat balance for cooling zone for the required product temperature Tutorial problem: Work out total heat balance for all the three zones, for 1kg (10 moles) of CaCO3

    Heat balance for calcination shaft furnace

    Roasting of sulfides
    Roasting is the oxidation of metal sulfides to metal oxide and sulfur dioxide ZnS + 3O2 = 2ZnO + 2SO2 2FeS2 + 5.5O2 = Fe2O3 + 4SO2 Additionally. Formation of SO3,metal sulfates and complex oxides such as ZnFe2O4 Typical ores sulfides of Cu, Zn & Pb Roasting below MP of sulfides & oxides (usually below 900-1000C, but above 500600C for sufficient velocity of reaction)

    Roasting of sulfides
    Thermodynamics of roasting 3 components, hence max of 5 phases. (i.e. 4 condensed + 1 gas phase) Gas phase normally contains SO2, O2 also SO3, S2 Following equilibria exist in gaseous components S2+ 2O2 = 2SO2 . (1) 2SO2 + O2 = 2SO3 . (2) For a given temp., gas composition is defined by partial pressure of the gasses. Also for a fixed gas composition, the composition of condensed phases is fixed. Thus phase relations in a ternary system at constant temperature can be defined by a 2D diagram

    Predominance area diagrams

    logpSO2

    logpO2

    Roasting of sulfides
    Lines that describe equilibrium between the three phases are defined by equationsMS2 (c) = S2(g) .(M is divalent) S2(g) + O2(g) = SO2(g) MS + 3/2 O2 = MO + SO2 SO2 + O2 = SO3 MO + SO3 = MSO4 MSO4 = MO.ySO3 + (1-y)SO3 MO.ySO3 = MO + ySO3

    Roasting reactions
    S2(g) + O2(g) = SO2(g) (1) MS + 3/2 O2 = MO + SO2 (2) At roasting temp., above reactions have large -ve free energy changes and SO2/O2 equilibrium is far right.
    At 1100K, the equilibrium constant for equation (1) is 1.2 x 1013 \ At this temperature, SO2 is stable phase, even at very small pO2

    Roasting reactions
    S2(g) + O2(g) = SO2(g) (1) MS + 3/2 O2 = MO + SO2 (2) At roasting temp., above reactions have large -ve free energy changes and SO2/O2 equilibrium is far right.
    E.g. in case of FeS, for reaction (2) DG (cal)= -113000 + 9.5T logT - 1.965(10-3T2) - 6.7T At 1100K, the equilibrium constant, K is 1.2 x 1018 \ sulfide is converted to oxide at relatively small pO2

    Roasting of sulfides
    For the given Me-O-S system diagramMe + SO2 = MeS + O2 2Me + O2 = 2MeO 2MeS + 3O2 = 2MeO 2MeO+2SO2+O2 = 2MeSO4 MeS+2O2 = MeSO4
    Additional equations may be required ifMeS2, Me2O3, Me2(SO4)3, MeO.MeSO4 exist

    Predominance area diagrams


    Me + SO2 = MeS + O2 ..(3) 2Me + O2 = 2MeO ..(4) 2MeS + 3O2 = 2MeO + 2SO2 ..(5) 2MeO + 2 SO2 + O2 = 2 MeSO4 ..(6) MeS + 2O2 = MeSO4 ..(7) The equilibria are given by the expressions Log pO2 log pSO2 = log K3 Log pO2 = log K4 2log pSO2 3log pO2 = log K5 2log pSO2 + log pO2 = log K6 2 log pO2 = - log K7

    Predominance area diagrams


    pS2 = 1atm logpSO2 pSO3 = 1atm

    logpO2

    Why Predominance area


    For a given metal, the form of equilibrium expression is the same for all metals The slope of corresponding curves in the diagram are same Only value of ks may differ This means that the positions of lines may change Consequently size and position of areas may change

    Predominance area diagrams


    These areas are called predominance area for the particular phase In this area, phases exist even though SO2 and O2 may be changed independent of each other There are 2 deg., 1 deg. and invariant regions Lines for reactions for formation of SO2 & SO3 S2+ 2O2 = 2SO2 . (1) 2SO2 + O2 = 2SO3 . (2) are given by the expressions 2 log pSO2 2 log pO2 = log K1 + log pS2 2 log pSO2 +2 log pO2 = - log K2 + 2log pSO3

    Creating predominance area diagrams


    Ni-S-O system at 1000K Condensed phases have Ni, NiO, Ni3S2, NiSO4 Gas phase SO2, O2 (some SO3 & S2) Consider reactions such as NiS(c) + 1.5 O2(g) = NiO(c) + SO2(g) .DG = 104.8kcal Likewise Ni3S2(c) + 3.5 O2(g) = 3NiO(c) + 2SO2
    DG=308.4kcal, and K = pSO22/pO27/2 \ logpSO2 = 7/4 logpO2 + log k .(BC) For which K = pSO2/pO23/2 and log pSO2 = 1.5 logpO2 + logK .(CD)

    Creating predominance area diagrams


    List all reactions and their equilib. Constants NiS + 1.5O2 = NiO + SO2 Ni3S2+3.5O2 = 3NiO + 2SO2 Ni + O2 = NiO (DG = -44.5kcal)..(AB) NiS + 2O2 = NiSO4 (DG = -125.8kcal)..(DG) 2NiO + 2SO2+O2= 2NiSO4 (DG = -32.6kcal) ..(DH) 3NiS + O2 = Ni3S2 + SO2 (DG = -72.3kcal) ..(FC) Ni3S2 + 2O2 = 3Ni + 2SO2 ..(EB)

    Creating predominance area diagrams


    1000 K
    G D C

    NiS
    log pSO2

    NiSO4
    H

    Ni3S2
    F E

    NiO

    Ni
    A log pO2

    Kellog diagram for Copper and Iron Sulfides


    Fe2(SO4)3

    log pSO2

    Cu Cu2O

    pS2 = 1atm

    Fe

    FeO Fe3O4

    log pO2

    Fe3O4 Fe2O3

    Cu2O CuO

    T=700C

    Effect of temperature on roasting equilibria

    Chloridizing roast
    To bring nonferrous metals into water soluble form MeS + 2NaCl + 2O2 = Na2SO4 + MeCl2 (10%NaCl/5600C) To convert nonferrous metals into volatile chlorides MeO + CaCl2 = MeCl2 (g) +CaO (1250C) MeS +CaCl2 + O2 = MeCl2(g) + CaO + SO2 MeO + Cl2 = MeCl2 (g) + O2 MeS + Cl2 + O2 = MeCl2(g) + SO2 (900-1000C) Iron oxide is not easily chloridised 3MeO + 2FeCl3 = 3MeCl2 +Fe2O3 This reaction is strongly shifted to the right

    Heat balance during roasting


    Oxidation of Cu2S in Air: Ref temp=25C = 298K. Cu2S(1300C) + (O2+3.76N2)(25C)=(2Cu+SO2+3.76N2)(1250C)
    Input Cu2S(l) O2 + 3.76N2 S(rh)*+O2=SO2 -DH298 Kcal/mole 30.0 0.0 71.0 Output 2Cu SO2 3.76N2 Cu2S=2Cu+ S(rh)*
    Heat surplus

    Kcal/mole 22.8 15.1 35.3 DH298 19.6 8.2 101.0

    Total Input

    101.0

    Total output

    Heat balance during roasting


    Oxidation of Cu2S in Air: Ref temp= 1300C = 1573K.. Cu2S(1300C) + (O2+3.76N2)(25C)=(2Cu+SO2+3.76N2)(1250C)
    Input 2Cu SO2 3.76N2 S2*+O2=SO2 Total input Kcal/mole 0.8 0.7 1.5 86.1 89.1 Output O2 3.76N2 Cu2S=2Cu+ S*(g) Heat surplus Total output Kcal/mole 10.3 36.8 33.8 8.2 89.1

    Heat balance during roasting


    Technology of roasting Multiple hearth furnace Flash roasting Fluidized bed roasting Sinter roasting

    Multiple hearth roasting

    Dwight Lloyd sintering machine

    Heat balance for pyrite(FeS2) roasting


    Oxidation of Cu2S in Air: Ref temp= 25C. (Surplus heat) (FeS2 + 4.13O2 +15.5N2)(25C)=(0.5 Fe2O3+2SO2+1.38O2+15.5N2)(900C)
    Input FeS2 4.13O2+15.5 N2 Fe+0.75O2=0. 5Fe2O3 2S + O2=SO2 Total input Kcal/mole 25C 25C 0 0 99 142 241 Output Kcal/mole 0.5Fe2O3 15.5 2SO2 + 15.5N2 H(1173) 123.1 +1.38O2 FeS2=Fe+2S Heat surplus Total output DH298 36.0 56.9 241

    -DH298 -DH298

    Reduction smelting
    Mineral + gangue + reducing agent + flux = metal/matte + slag + gas Fluxes Slags Reducing agents
    C, H2, Reactive metals(Al, Ca)

    slags
    Vitreous by-product of smelting Collects unreduced gangue in a separate layer Provides a medium to collect impurities
    Synthetic slags

    Should have large difference in sp.gv Should be fluid enough Contains oxides, silicates, metals and sometime sulfides Metal loss in slag Basic(O2-, SiO44-)/Neutral(SiO44-)/ Acidic(chain silicate anions- Si2O67-, Si3O108- & ring silicate anions Si4O128 Silicate degree = moles of acidic O2 from SiO2/ moles of basic oxygen from CaO, MgO, FeO
    (<1) (=1) (>1)

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