PGDIIPENG INTRO.

TO PYROMETALLURGY (FERROUS)

DR. ELIAS MATINDE (PR.ENG.)

©EMATINDE2018

Dr. ELIAS MATINDE

 Declaration
2

These notes are available only for academic purposes at

Wits. Except for the indicated use, these notes, or part
of thereof, may not be reprinted, reproduced, transmitted,
or utilized in any form without consent or
acknowledgement from the School of Chemical and
Metallurgical Engineering.

©EMATINDE2018
 Reference texts
3

1) Biswas, A.K. (1981). Principles of Blast Furnace

Ironmaking: Theory and Practice. Cootha Publishing
House. Brisbane, Australia
2) Seetharaman, S., Mclean, A., Guthrie, R. and
Seetharaman, S. (2014). Treatise on Process Metallurgy,
Volumes 3: Industrial Processes, Part A. 1st Edition
3) Ndlovu, S., Simate, G.S. and Matinde, E. (2017). Waste
Production and Utilization in the Metal Extraction Industry.
CRC Press Boca Raton
 Overview
1.4 Overview of pyrometallurgical processes

2. Thermodynamic and kinetic considerations

3. Carbon reductants in metallurgical processing

4. Blast furnace iron making processes

5. Steelmaking processes

6. ferroalloy production processes

 Overview: Why pyrometallurgy
5

 Some reactions are only possible only at high

temperatures (thermodynamically).

 Reaction rates generally higher at higher temperatures

(kinetically)

 Several phases available to effect separation of elements:

slag (molten oxides), molten metal, and gas

 Effective and low cost reagents available for reduction

(e.g. carbon) and oxidation (e.g. oxygen).
 Overview
6

 Most pyrometallurgical smelting and refining operations

can be considered as multi phase (gas-solid and liquid)
reactions

 Smelting and refining reactions are conducted at high

temperatures, with a significant proportion of reactants
and products in the liquid state

 Carbon reductants play a critical role in pyrometallurgical

processes (thermal, chemical, physical)
 Unit processes in pyrometallurgy
7

 Reduction (gas-solid and solid-liquid reactions)

 Melting: molten phases

 Extraction: gangue separation; crude alloy product

 Refining and alloying: impurity removal and alloy chemistry

adjustment

 Casting: conversion into appropriate physical and intermediate

condition
 Unit processes (typical)
8

 Extraction and refining processes→ Meltdown of solids in

conjunction with separation from non-values + refining
1. Smelting of oxides →smelting reduction processes,, blast
furnace ironmaking,
2. Scrap-based smelting processes, e.g. EAF
3. Ferroalloys smelting and refining processes →SAF, converter
refining
4. Refining of molten steel to produce final alloys→ BOF, AOD,
ladle metallurgy
5. Clean steel strategies →inclusions control
6. Casting and solidification: Continuous casting,
 Kinetic and thermodynamic considerations
9

 Typically, pyrometallurgical processes involve:

1) Chemical reactions (multi-phase)
2) Kinetics of chemical reactions
3) Physicochemical processes: viscous flow, interfacial
phenomena, mass transfer

 Chemical thermodynamics:
1) Reaction free energies and enthalpies
2) Chemical equilibrium
 Process phenomena
 Kinetics of multi-phases (gas-liquid, solid-liquid, gas-solid, and
10
liquid-liquid) reactions, with emphasis on the effects of gas flow
 Reactions in process metallurgy are manipulated in several
fundamental ways →effect on reaction equilibrium state of
reactions
 Temperature
 Redox conditions (e.g., concentrations of reducible species such as FeO
content of slag, or of reactive elements such as deoxidizers dissolved in
liquid metal
 Activity and activity coefficient of species dissolved in slag (affected by
slag basicity)
 Mass balance (e.g. relative masses of slag and metal)
 Gas phase: change in total pressure, dilution with inert gas
 Reaction kinetics: stirring, particle size and porosity (gas-solid
reactions), heat transfer rate, reactor size and shape, and fluid
flow
 Blast furnace iron making
11
 Multiphase phenomena in ironmaking
12
 Submerged arc furnace
13
 Multiphase phenomena in SAF (HCFeCr)
14
 SAF of HCFeCr
15
High temperature zones: slag-metal reactions
16
 Multiphase phenomena in SAF (HCFeMn)
17

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Reaction zones in the SAF
18
 Reaction zones in the SAF
19

 Modelling the tapping process in SAF in HCSiMN. ISIJ 2011 (2): 193-202
 Coke bed in SAF
20

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Coke bed in SAF processing of FeMn
21

Sketch of a 75 MVA HCFeMn furnace cut through one electrode (Barcza et al. 1979).
 Coke bed in SAF: Simulations
22
 Flow of slag in coke bed (FeMn)
23

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Heterogeneous reactions → slag-metal-gas
reactions in oxygen steelmaking
24

 Kinetics: Large surface area in the emulsion (slag-metal-gas

mixed phases
 Heterogeneous reactions → slag-metal-gas-
refractories reactions in ladle refining
25
 Kinetic and thermodynamic considerations
26

 Thermodynamics and kinetics are important tools in high

temperature extraction metallurgy
 Thermodynamics → feasibility of processes or reactions +
driving force governing the rates (kinetics) of such reactions)
 Assumption 1: Pressure and temperature are constant→ study
equilibria at the interface of between two and more phases,
e.g. slag-metal, refractory-metal, inclusion-metal or
atmosphere-metal
 Assumption 2: Chemical reactions are not rate limiting due to
high temperatures and correspondingly high reaction rates
 Mass and heat transfer to and from the interfaces determine
the kinetics
Thermodynamics of melts: Henrian solutions
27

 Molten metal: dilute solution of atoms of iron (as solvent)

and atoms of the alloying elements (solutes) and impurities,
e.g. Mn, O, C, Si, Cr, P, S, etc
 Treatment of dilute solutions simplified by Henry’s law: the
activity of any component at infinite dilution is equal to its
concentration, hi= [wt. % i]
 Henrian activity description:
 Activity of species= (mass %) x (activity coefficient),
e.g. hC =fC[%C]
 Activity coefficient dependent on the all other dissolved
elements
 Thermodynamics of melts: Raoultian & Henrian
melts
28

 For an ideal solution (obeying Raoult’s law): ai = Xi

 Most real solutions do not obey Raoult’s law (negative or
positive deviation)
 Liquid steel technically fall in the category of dilute
solutions where the concentrations of solutes (C, O, Si, Mn,
S, P, etc.) are mostly below 1 wt. % (exception high alloy
steels).
 Thermodynamic parameter→𝛾𝑖 which is the activity
coefficient of component i in a solution.
 Solutes in binary solutions obey Henry’s law→𝑎𝑖 = 𝛾 0 𝑖𝑋𝑖
→ Henry's law constant
 Thermodynamics of melts: Raoultian &
Henrian melts
29

 Activities of dissolved elements in liquid steel are

expressed with reference to Henry's law (WHY?)
 For binary Fe-i solution:

1. Henry’s law is obeyed by the solute in the binary Fe-i

solution→ hi = Wi
2. Henry’s law is not obeyed by the solute, i, then→ hi = fi
Wi
where fi is the activity coefficient in the one wt. % standard state
 Activities in the gas phase
30

 Gas phase→ mixture of neutral atoms and molecules

 Near ideal conditions
 Raoultian activities description→ Activity of species=
partial pressure

pCO  X CO  ptot

Total pressure
Mole fraction in the gas
 Decarburization of stainless steel involving the slag phase
31

Reaction ΔG0 (J/mol)

1 -114 400 – 85.77T

𝑂2(𝑔) + 𝐶 = CO(𝑔)
2
[𝐶] = 𝐶 22 590 + 4226T
3
𝑂 + 2[𝐶𝑟] = 𝐶𝑟2 𝑂3(𝑠𝑙𝑎𝑔) . -1 110 000 + 247.0T
2 2(𝑔)

2[𝐶𝑟] = 2𝐶𝑟 -38 500 + 93.7

• Show that the slag-phase decarburization reaction is represented as by
𝐶𝑟2 𝑂3 (𝑠𝑙𝑎𝑔) + 3 𝐶 = 2 𝐶𝑟 + 3𝐶𝑂(𝑔)
• Calculate the Gibbs free energy of reaction
• Show calculate the temperature dependence of the equilibrium constant
(𝑎𝐶𝑟 )2 (𝑝𝐶𝑂 )3 −88704
(i.e. 𝑙𝑛 𝐾 = 𝑙𝑛 = + 56.67)
(𝑎𝐶 )3 𝑎𝐶𝑟2𝑂3 𝑇
 1st Law of thermodynamics
32

 Modelling energy and material balances in metallurgical

reactors
 Assuming steady state conditions:
Qcv   ni  h0o  h   Wcv   n j  h0o  h    Qloss
R i P j

 Where, is the system being examined; if the flow of heat through the
system; W is work done by the system; R and P are the reactants and
the main products, respectively; n is number of moles; is standard molar
enthalpy; is the change in molar enthalpy; represent the heat losses
from the system; i and j are the indices for the reactants and products,
respectively
 1st Law of thermodynamics: Heat capacity
33 Quantity of heat q required to raise the temperature by
1°C →extensive quantity depending on the amount of
𝜕𝑞
substance→ 𝐶 = ( )
𝜕𝑇
 Molar heat capacity→ intensive property
𝜕𝑞 𝜕𝑈
 Constant volume: 𝐶𝑉 = ( )V=( )𝑉
𝜕𝑇 𝜕𝑇
𝜕𝑞 𝜕𝑈
 Constant pressure: 𝐶𝑉 = ( )P=( )𝑃
𝜕𝑇 𝜕𝑇
∗
 Ideal gas: 𝐶𝑃 − 𝐶𝑉 = 𝑅 ,
3
where 𝐶𝑉 = 𝑅 = 12.47𝐽𝑚𝑜𝑙 −1 𝐾 −1
2
5
and 𝐶𝑃 = 𝑅 = 20.79𝐽𝑚𝑜𝑙 −1 𝐾 −1
2
 1st Law of thermodynamics- temp. dependence
 Temperature dependence of CP:
34

CP  a  b 103 T  c 105 T 2  d 106 T 2 ; J / mol  K

 Specific heat capacity (CP) and molar enthalpies:

T
h  hT  h298  C
T0
P dT  h phase ; kJ / mole

CP  a  b 103 T  c 105 T 2  d 106 T 2 ; J / mol  K

 Where and are the enthalpies at temperature T and at 298K;
is the specific heat per mole at constant pressure; is the change
in phase enthalpy per mole; K, a, b, c, and d are constants for
the respective components of the system.
e.g. Typical thermodynamic system in steel refining
35
 1st law of thermodynamics (cont.)

36
BF → continuous countercurrent reactor at steady state:
heat transfer through granular bed
 Mass balance:
 m m  m  m
IN  ....  m
Scrap m  Fluxes Oxygen DRI PCI

 m  m  m  .....  m  m
OUT HM Slag Dust Ironin slag

 Heat of reaction:
H R   H f ( products )   H f (reduc tan ts )

 Molar enthalpies:
HTo 
ni
t
 H 298
o
( products) 
ni
t
 H 298
o
(reac tan ts) 
ni
dt 
298
T
 CP ( products)   CP (reac tan ts)  dT 
 Molar enthalpy/ssensible heat:
Tm Tb T
H T  H 298  C
298
p ( s )dT  H m   C p (l )dT  H v   C p ( g )dT
Tm Tv
 1st law of thermodynamics-mass balance

37
BF → continuous countercurrent reactor at steady state:
heat transfer through granular bed
 Mass balance:
 m m  m  m
IN  ....  m
Scrap m 
Fluxes Oxygen DRI PCI

 m  m  m  .....  m  m
OUT HM Slag Dust Ironin slag

 Heat of reaction:
H R   H f ( products )   H f ( products )

 Molar enthalpies:
HTo 
ni
t
 H 298
o
( products) 
ni
t
 H 298
o
(reac tan ts) 
ni
dt 
298
T
 CP ( products)   CP (reac tan ts)  dT 
 Molar enthalpy/sensible heat:
 Tm Tb T 
H T  H 298  ni   C p ( s )dT  H m   C p (l )dT  H v   C p ( g )dT 
 298 Tm Tv 
 Gas solid reactions
38

 Solid state diffusion is slow (and can be neglected)

 Fast reaction in porous solids (e.g. sinter, iron ore, coke) due
to fast diffusion of gases (and liquids) through the pores.
 Gas-solid reactions
 Solid state reduction and Boudouard reactions are typical gas-
39
solid reactions
 Common feature of gas solid reactions

 Gaseous diffusion (mass transfer) of reactants and products

from bulk of the gas to the internal surface of the reacting
solid particles.
 Diffusion of gaseous reactants or gaseous products through the
pores of a solid reaction product or though the pores of a
partially reacted solid.
 Adsorption of the gaseous reactants on and desorption of
reaction products from solid particles.
 The actual chemical reaction between the adsorbed gas and
solid
 Typical solids reactions in pyrometallurgy
40

Reaction ΔH0 (kcal/g-mol X)

C(s) + O2(g)→CO2(g) -94 052kcal/g-mol C

FeO(s) + C(s) → Fe(s) + CO(g) +37 884kcal/g-mol

FeO
FeO(s) + CO(g) → Fe(s) + CO2(g) +37 884kcal/g-mol
FeO
FeO(s) + H2(g) → Fe(s) + H2O(g) +6 502 kcal/g-mol FeO

FeS2(s) + 11O2(g) → 2Fe2O3 (s) + 8SO2(g) -197 650 kcal/g-mol

FeS2
C(s) + CO2(g) → 2CO(g) + 41 220 kcal/g-mol C
 Typical metal-gas reactions (refining)
41

 Decarburization and hydrogen removal

C steel  O steel  (CO ) gas

 H steel   H steel  ( H 2 ) gas

 Slag-metal reactions
42

 Refining functions of slags

 Redox (oxidation-reduction) reactions , e.g. desulphurization
[S]steel → (S2-) slag

 For charge balance → oxygen anion in slag and dissolved

oxygen in steel

[S]steel + (O2-)slag → (S2-)slag + [O]steel

 De-S depends on both slag basicity (O2-) and redox conditions

(given by [O]steel)
 Kinetic considerations
 Iron and steel making processes are carried out at high
43
temperatures where the kinetics of reactions are fast and
chemical equilibria is easily attained.
 Heterogeneous reactions (gas + solid +liquid phases)

 Reactions take place at the phase boundaries/ interfaces

and involves the transport of reactants to the interface and
reaction products away from the interface (mass transfer).
 Mass transfer in the bulk phase away from the interface- is
sufficiently rapid in mixed fluids and under turbulent flow.
 Mass transfer at or near the interface → dependent on the
concentration at the interface, temperature, surface area, etc.
Kinetic steps: (1) interfacial chemical reaction, (2) mixing in
the bulk fluid, and (3) mass transfer at/near the near
interface
 Unit Processes: Iron and steelmaking
45

 Iron and steel making processes: gas-solid and solid liquid

reactions
 Conditions: temperature, slag basicity, redox, slag volume,
stirring intensity
 Unit Processes
 Blast furnace ironmaking
 EAF steelmaking
 BOS steelmaking
 Secondary/ladle metallurgy
 Solidification and casting
 Overview: unit processes
46
 Objectives of iron and steel making
1. Converting of cold iron ore (96% Fe2O3, 5 % SiO2, 1 %
47
Al2O3, 0.05 % P) to on-specification liquid steel, e.g.
0.06%C, 0.014%P, 0.005%S, 0.005%N, 0.03%Al)
 Required steps and inputs:
 Energy (from C, O2, electrical)
 Reductants for removing oxygen from hematite (coke, coal)
2. Removal of impurities originating from raw materials
 SiO2 (fluxes)→slag (blast furnace, steelmaking)
 P (CaO, oxygen) →slag (steelmaking)
 S (CaO, reductant, CaC2) →slag (BF, HM de-S)
3. Removal of dissolved elements
 C (+O2) →CO (steelmaking) 19/02/2018
 O (+Al) →Al2O3 (ladle)
 Al2O3 →slag (ladle)
 Al2O3 (+Ca) →liquid slag aluminates (ladle)
 Main process steps
 Blast furnace-Basic oxygen steelmaking route
48
Process step Main product
→Blast furnace Hot metal: Fe-4% C, 1%S
→Hot metal de-S as above, lower S
→Steelmaking Fe-0.04% C, 0.05%S
→ Ladle metallurgy as above, O removed
→Continuous casting as above, solid
 EAF route
→DRI + Scrap DRI: Fe, some FeO
→ EAF Fe-0.04%C, 0.05% S
 Main process steps
49

 EAF steelmaking route

Process step Main product
→DRI + Scrap DRI: Fe, some FeO
→Hot metal de-S as above, lower S
→Steelmaking Fe-0.04% C, 0.05%S
→ Ladle metallurgy as above, O removed
→Continuous casting as above, solid
 Blast furnace iron making
50
 Blast furnace zones
 Primary reduction zone → Upper part of the shaft, reduction
51
of higher valence iron oxides (Fe2O3 & Fe3O4). Temperature
range 400-1000°C
 Thermal reserve zone → Lower part of the shaft, temperature
maintained around 800-1000oC. Reduction of wustite (FeO) to
metallic iron
 Cohesive zone → Extending to above the bosh near the wall
and up to the middle part of stack in the centre of the furnace.
Softening and melting of burden materials (exception coke).
Temperature around 1200°C
 Active coke zone/dripping zone → Beneath the cohesive zone.
Final reduction to metallic iron. Melts of slag and metal and
dripping of melt through the coke zone
 Deadman zone →Porous packed-bed of unreacted coke
particles floating in the hearth. Carbon saturation of hot metal
takes place
 Rate phenomena in ironmaking
52

 C-CO-CO2 thermodynamic system

 Fe-C-O thermodynamic system

 C-H-O thermodynamic system

 Rate phenomena and rate laws

 Reducibility and degree of reduction

 C-CO2-CO thermodynamic system
 Combusts with O2 in the preheated air blast at the tuyere zone
(temps. 1900-2000°C)→combustion products CO, CO2 and
53 N2 travel upwards through the countercurrent solids bed
 C-H-O thermodynamic system

55
 Rate phenomena: Granular zone
56
Uniform internal reduction vs. topochemical reduction

Uniform
57 internal reduction:
diffusion through the pores is
faster than chemical reaction
(smaller particle size, high
porosity)
 Carbon composite agglomerates

58
 Rare of reduction and reducibility (F0)
𝐿𝑜𝑠𝑠 𝑜𝑓 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑜𝑟𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑟𝑒𝑚𝑜𝑣𝑎𝑙 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛
 Reducibility: 𝐹0 =
59 𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑚𝑜𝑣𝑎𝑏𝑙𝑒 𝑜𝑥𝑦𝑔𝑒𝑛 𝑖𝑛 𝑜𝑟𝑒
𝑑𝐹0
 Rate of reduction, r0= → measure of reducibility
𝑑𝑡
1
[1− 1−𝐹0 3 ]
 𝑟0 = = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑡
 For CO reduction of FeO:
𝑝𝐶𝑂2
FeO(s) + CO(g) =Fe(s) + CO2 (g) → 𝑟0 = 𝑘𝑐 (𝑝𝐶𝑂 − )
𝐾1
For H2 reduction of FeO:
𝑝𝐻2𝑂
FeO(s) + H2(g) =Fe(s) + H2O→ 𝑟0 = 𝑘𝐻 (𝑝𝐻2 − )
𝐾2
Where kC and kH are rate constants, and K1 and K2 are
equilibrium constants for the reactions
 Coke and coal in metallurgical industry
60

 Coal and carbon → reductants (chemical function)

 Fuels- thermal functions
 Conductor of electricity → coke bed in SAFs
 Aerodynamic and permeability support (structural support) →
blast furnace + SAFs (coke bed)
 Sintering process (coke breeze) → agglomerating ore fines
 Slag foaming → EAFs
 Coke and coal in metallurgical industry
61

 Reductants
 Blast furnace → Coke, form coke, briquettes, pulverized
coal (PCI)
 Submerged arc furnace (SAF): → Coke, char, anthracite,
charcoal, petroleum coke, graphite, form coke, briquettes
 Direct reduction → Pulverized coal, gasified coal,
charcoal, anthracite coke petroleum coke
 Conductants → Electrode fillers- calcined anthracite,
graphite
 Refractory materials → Graphite, graphite paste,
ramming paste
 Thermal functions
62
 Types of coal
Organic composition and nature of coal
63

 Three groups of organic fragments → macerals

1. Vitrinites
Order of increasing
2. Intertinites
carbon content
3. Liptinites
 Macerals and maceral groups differ in chemical

composition + technical performance characteristics → the

macerals of the liptinite group contain more hydrogen and
are more generally reactive than the macerals of the
inertinite group, while vitrinite group macerals range
between the two.
 Common minerals found in coal
64
 Metallurgical coke
 Metallurgical coke is a macro porous carbon material of high
65 strength produced by carbonization of coals of specific rank or

of coal blends at temperatures up to 1400 K.

 Fuel function→ Provides heat for the endothermic requirements
of chemical reactions and the melting of slag and metal
 Chemical function → Reducing agent C and CO gas to reduce
iron oxides
 Carburization function → Reduces the melting point of metallic
iron
 Mechanical support → Permeable support it acts as the only
solid material in the furnace that supports the iron bearing
burden and provides a permeable matrix necessary for slag
and metal to pass down into the hearth and for hot gases to
pass upwards into the stack.
 Aerodynamic function → coke layers act as a gas distributor
Diez et al. (2002). International Journal of Coal Geology 50: 389-412
 Metallurgical grade coal
66

 Coal blend design to satisfy coke

physical properties.
 Coal blend design to satisfy coke
chemical properties.
 Coal blend design to satisfy coke
oven pushing performance.
 Coal blend design to satisfy
maximum usage of low value
carbon materials.
 Economic evaluation of the
designed blend.
 Assurance of high quality coal
shipments.
 Metallurgical coke
Blend of different coking coal grades
67

 Other additives and recycled materials added to coal

blends
 Blending → balance of desired properties of coke +
stable operation of coking plant + cost
Properties of coking coals
 Physical properties → density, grain size, petrography, ash,
volatiles, moisture
 Chemical properties → P, S, K and Na contents, ash
composition, fixed carbon
 Coking properties → plasticity, shrinking, swelling
 Quality → stability and consistency of the quality properties
 Characterization of metallurgical coke
68
 Characterization of metallurgical coke
69
70
 Degradation of coke in the blast furnace

72
 Degradation of coke in the blast furnace

73
Li et al., (2014). Fuel 133: 194-215
74
 Ferrous burden (raw materials)
75

Treatise on Process Metallurgy Volume 3

 Metallurgical tests for iron ores
76 Physical properties
 Tumble strength→ tumble index + abrasion index
 Abrasion index
 Shatter index
 Apparent porosity
 Thermal degradation
 Metallurgical properties
 Reducibility
 Low temperature disintegration
 Reduction swelling behavior
 Reduction under load
Muwanguzi, A.J.B., Karasev, A.V., Byaruhanga, J.K. and Jonsson, P.G. (2012). Characterization of the physical
and metallurgical properties of natural iron ore for iron production. ISRN Materials Science:1-9
 Blast furnace sinter
 Sintering: Process of fusing iron ore fines into larger
particles suitable for charging in the blast furnace.
 The iron ore reacts with fluxes to form a multi-phase
compound (sinter) that mainly contains hematite, magnetite,
SFCA (silico-ferrites of calcium and aluminum) and calcium
silicates.
 The SFCA phase is the bonding phase. Sinter can withstand
pressure and temperature conditions when charged in the
blast furnace.
Advantages of Sinter
 Use of iron ore fines, coke breeze, metallurgical wastes, etc.
for hot metal production
 Better reducibility (Fe2O3 →Fe3O4 transformation) and
other high temperature properties
 Reduced coke rate (sinter contains coke breeze)
Sintering process: incipient fusion of phases
Gas flow
78 Ore
Ore

(a) Before sintering (b) After sintering (liquid phases solidified)

 Sinter properties
79

 Chemical composition and pore structure effect on HTRPs: Affects

liquid phase amount, viscosity and melting and reduction rate of
slag coexisting with hot metal and containing low FeO → affects
carburization behavior of hot metal, which in turn affects the
dripping properties of metal

 Chemical composition, pore structure and mineralogy effects on

softening and melting temperature of sinter →low liquidus
temperature of slag and reducibility of slag containing high FeO

 High Fe content of sinter, C/S ratio (1.5-2.0) and low Al2O3→ ↑the
HTRPs of sinter
 Sinter mineralogy
80

 Sinter mineralogy and microstructure → physical and

metallurgical properties
 Sinter phases
 Primary phases → unreacted and partially reacted
hematite, magnetite and remnant fluxes
 Secondary phases → silico-ferrites of calcium and
aluminium (SFCA), secondary hematite and magnetite,
and glass phases
 SFCA → sinter bonding phases. Interlocked and porous
microstructure → strength and reducibility.
Sinter mineralogy
81

Hematite sinter structure,

showing remnant hematite
nuclei, the melt-derived
matrix and porosity
 Blast furnace pellets
 Iron ore pellets are used for the production of hot metal in the
82 blast furnace and DRI/HBI in direct reduction processes.

 Main types of pellets

 Acid pellets
 Basic pellets
 Fluxed pellets
 Fluxes/additives are used to produce better metallurgical
properties (i.e. reducibility, softening and melting, slag
formation), →e.g. limestone (CaCO3), Magnesite (MgCO3)
dolomite ((Ca,Mg)CO3), olivine (Mg2SiO4)
 Characterization tests for iron ore pellets
83
 Pellets properties: Summary
84
 Chemical composition (→ slag volume) → acid vs. basic fluxed
pellets
 Induration properties → bonding phases
 Cold strength→ compression strength and fines generation
during tumbling
 Reduction-disintegration properties
 Swelling properties → ISO 4698 → transformation of wustite
to metallic Fe → low compression strength and generation of
fines
 Softening and melting phenomena → implications ?

Ref: Nogueira, P.F. and Fruehan, R.J. (2004). Blast furnace burden softening and melting
phenomena Part 1: Pellet bulk interaction observation. Metallurgical Transactions 25B: 829-838
85
 Blast furnace physicochemical zones
86
 Blast furnace physicochemical zones
87

Indirect
reduction zone

Thermal and
chemical reserve
zone
Direct reduction
zone
Solution loss
FeO+C  Fe+CO
C+H2O  CO+H2
reaction
Desulphurization +
1  CO
C+ --O
Carburization
2 2
 Blast furnace physicochemical zones
88
 Zones and functional structuring of the BF
Li et al., (2014). Fuel 133: 194-215

89
Blast furnace tuyere and raceway zones

90
Physical raceway→ defined by stagnant coke
 Chemical raceway → where neither CO2 and H2O exist
 Raceway adiabatic flame temperature → typical control
measure
Blast furnace tuyere and raceway zones

91
A typical raceway is 0.8-2m long (depends on design
and size of BF)
 In the raceway, the penetrating jet expands, mixes with
hearth gas and coke building a whirling cavity where the
coke carbon, injected fuel and hearth atmosphere react
with hot blast.
 Factors influencing the raceway length:
 Jet velocity → too high velocity → jet mill grinding effect
on coke→ effect on coke strength (?)
 Rate of injected auxiliary fuels →shortens the raceway
(detected by increasing thermal load on bosh lining)
 Oxygen enrichment → lengthens the raceway
 Deadman →inactive Deadman steers the gas flow toward
the bosh walls → affects the material flow and gas
distribution
 Cohesive zone
 Active coke zone + dripping zone : intensive contact between
92
the counter current gas and solid coke, molten metal and
molten slag
 Slag rate and slag viscosity effects to flow conditions : high
slag rate and high viscosity slag may result in flooding (Effect
on gas flow?)
 The cohesive zone in the blast furnace is the zone in which the
burden starts to soften up to the smelting zone. It extends from
the bosh to the lower shaft, and is located between the
softening and melting isotherms
 Carburization of iron layer flowing between the coke windows

 Narrow cohesive zone favorable for the furnace operation

(WHY?)
 Cohesive & dripping zones
93

Discuss the behavior of ferrous burden in the

following zones:
 Softening and melting zones (upper part
of cohesive zones)
 Dripping zone

 Correlate your responses to the following

Behavior and properties of coke
 Permeability and permeability resistance
of the burden
 The Cohesive Zone
94
Position of the cohesive zone
influences:
 The gas distribution;

 The permeability resistance and

 The heat requirements of the

lower furnace

 In collorary, what are the factors

that affect the position of the
cohesive zone?
 Fluid flow phenomena in cohesive zone
95

 Softening and melting of

ferrous burden and slag
formers → gas
permeability becomes
poor, and the heat
exchange efficiency
decreases.
 The formation of molten
slag and molten iron need
to be enhanced for better
energy efficiency of the
blast furnace
 Burden softening and melting phenomena
96

Kaushik, P. & Fruehan, R.J. (2006). Ironmaking and

Steelmaking 33 (6): 507-519
 Blast furnace thermal balance
97

 Functions of the blast furnace:

 Heat exchange → countercurrent flow of solid burden and hot
reducing gases
 Oxygen exchange → oxygen transfer from solid oxides to gas
 Temperature effect on reaction equilibria and rates,
softening, melting and gasification
 Efficient blast furnace operation → fluid, free-running slag
 Critical hearth temperature → minimum hearth
temperature (1400-1450oC)
 Tuyere flame temperature → 1900-2200oC
 Blast furnace thermal balance
98

 Control of TFT
 Too high → formation of FeO-rich slag in the upper part before
the entire FeO gets reduced. FeO reduction → affects the slag
chemistry and viscosity
 High temperatures favor the reduction of SiO2 → high Si content
in hot metal → ↑costs of desiliconization (steelmaking)
 ↑ in vaporization of alkalis → ↑ alkali vapor recirculation
 Control of TFT is more of experience and art!
 Raceway adiabatic flame temperature (RAFT) → furnace
control
 Oxygen enrichment → ↑RAFT
 Endothermic decomposition of injectants and water-gas shift
reaction ↓ RAFT
 Summary
99
 Burden softening and melting phenomena in cohesive zone
1) Nogueira, P.F. and Fruehan, R.J. (2004). Blast furnace burden softening and melting phenomena Part 1:
Pellet bulk interaction observation. Metallurgical Transactions 25B: 829-838
2) Kaushik, P. & Fruehan, R.J. (2006). Ironmaking and Steelmaking 33 (6): 507-519
 Primary slag formation
 Effect of the position of the cohesive zone (viz. gas
distribution, permeability resistance, and thermal
requirements of the furnace)
 Factors affecting the position of the cohesive zone
 Heat, solids flow, fluid (gas + liquid) flow and permeability in
cohesive → multiphase flow, i.e. counter-current, co-current
and/or cross current flow of gas, powder, liquid and solid
phases → gas flow and permeability, chemical and heat
transfer
 Typical Material Balance

100

Inputs
 Ore: 63~65% Fe (lumpy ore)
 Sinter: 58% Fe, 5% SiO2, 9% CaO, 1~2% MgO, 1% Al2O3
 Coke: 88% C, 0.3% H2O, 10% Mineral Matter
 Coal (PCI): 80% C, 5% H2, 6% O2, 1% N2, 1% S, 5 %
Mineral matter

Output
 Pig Iron: 94.6% Fe, 4.6% C, 0.3% Si, 0.2% Mn, 0.02% S,
0.08%P
 Slag: 42.5% CaO, 35.5% SiO2, 7.5% MgO, 10.5% Al2O3,
0.2% Fe, 1% S
 Top Gas: 22% CO, 22% CO2, 4% H2, 52% N2
Material and energy balance (Treatise volume 3)
101

Treatise on Process Metallurgy Volume 3

 Material Balance
A blast furnace produces 2000 tons of pig iron a day. The
composition
102 of pig iron is as follows: C :4.0%, P :0.3%, Mn: 1.0%,
Si: 1.7%, S: 0.04% and Fe: Rest. The raw materials used and their
composition are as follows:
Iron Ore: Fe2O3 (88.5%), SiO2 (3.0%), Al2O3 (4.0%), P2O5 (0.5%),
H2O (4.0%)
Flux: CaCO3 (75%), MgCO3 (16.8%), SiO2 (5%), Al2O3 (2%)
Mn Ore: MnO2 (52%), Fe2O3 (41%), SiO2 (5%), Al2O3 (2%).
Coke: C (72%), SiO2 (1.5%), Al2O3 (8%), FeS (2%), Fe2O3 (3%).
Amounts of flux, Mn-ore, coke and quartz (SiO2 only) used per ton
of pig iron are 350kg, 60kg, 850kg and 80kg, respectively.
Calculate
(a) the amount of iron ore used per day assuming 99.80% of iron
charged goes into pig iron,
(b) (b) the weight of the slag phase
 Mass Balance Involving Multiple Streams
Solution
Let
a103
i, bi, ci and di denote the weight percent of the constituent elements of the i
th

element in the ore, blast, coke, and flux, respectively

A, B, C, and D denote the respective weights or quantities of the feed
ui, vi, wi denote the weight percent of the constituent elements of the ith element in
the metal, slag and gases, respectively
U, V and W denote the respective weights or quantities of the products
Assumptions
 The metal contains no Al, Ca, H, N and O
 All the phosphorus in feed enters the metal
 Sulphur partitions between the metal and slag
 The gases contain no metal bearing species
 Set up mass balance equations for constituent elements. Note that the
compositions are reported in weight % of the species present.
 Mass Balance Involving Multiple Streams
 Set up mass balance equations for constituent elements. Note that the
104
compositions are reported in weight % of the species present.
Material Al Ca C Fe H Mn N O P S Si

Ore aAl - - aFe aH aMn - aO aP aS aSi

Blast - - - - bH - bN bO - - -

Coke cAl - cC cFe cH - - cO - cS cSi

Flux - dCa dC dFe dH - - dO - - dSi

Metal - - uC uFe - uMn - - uP uS uSi

Slag vAl vCa - vFe - vMn - vO - vS vSi

Gases - - wC - wH - wN wO - - -
 Example

105
A blast furnace makes hot metal containing 3.6 wt. %C, 1.4 wt.
% Si, the rest being Fe. Other data include:
 Ore contains 85% Fe2O3, the remainder being 15% gangue of
SiO2 and Al2O3.
 Coke contains85% fixed carbon and 15% ash
 Coke consumption is 800kg per ton of hot metal
 Flux contains 95% CaCO3 and the remainder is SiO2, and its
consumption rate 400kg/t hot metal.
 The blast furnace top gas contains a ratio of CO/CO2 = 28/12
 Calculate pet ton of hot metal:
1) The weight of the ore used
2) The weight of slag produced
3) The volume of the BF gas
 Example
 An ore with the following composition is reduced with 10%
106

excess carbon at 1500°C to produce a metal (alloy) phase

with a saturated carbon (in the form of Fe3C and Mn3C in
the metallic phase) .Assume Fe is not lost to the slag and
10% of Mn element (in the form of MnO in the slag) is lost
to the slag. If 1000 kg ore is used, calculate the following:
1) The amount and composition of metal (alloy) phase
produced.
2) The amount and composition of slag phase produced
3) The total amount of carbon used in the process.
Composition of the ore: Fe2O3: 10 % FeO: 20 % MnO2:
50 % SiO2: 10 % Al2O3: 5% MgO: 5 %
Carburization +Formation of Hot Metal
 Metallic iron: gas-solid reduction → carburization of iron
107
at relatively low temperatures in contact with CO gas.
 Dissolution of C in solid Fe or sponge Fe lowers m.p. of

Fe→ C content in the iron in the shaft does not exceed 1

wt. % due to the slow kinetics of solid-solid reaction
 Carburization by solid coke becomes dominant at
temperatures > 1000°C
 Carbon content in the belly: 3-3.5 wt. % C

 Dripping zone →partially carburized liquid Fe flows

through the coke bed
 Hearth → carbon pick up by hot metal →carbon
saturation @4.5 wt. % C and temperature 1500oC
 Carburization reactions in BF
Eutectic point 4.3 wt. % C → temperature drop from 1536°C to
1153°C
108
 Fe-C-O system: Gas-based carburization
109
 Role of coke: Carburization in BF cohesive zone
110

(Ohno, K., Miki, T. and Hino, M. (2004). Kinetic

analysis of iron carburization during smelting
reduction. ISIJ International 44 (12): 2033-2039
 Pulverized coal injection in blast furnace
 PCI → injecting large volumes of fine coal granules into the BF
111
→supplemental carbon source → reduction of coke rate
→reduced pig iron costs
 Coke provides physical support and gas permeability in the BF
→complete substitution of coke is not possible.
 The amount of coal → depend on the coal and coke quality,
furnace geometry, and operational practices.
 The maximum level of coal → around 0.27 t/t-Hot Metal(HM).
The use of oxy-coal enables around 20% increase in coal
injection and help reduce coke quantities
 With 170 - 200 kg/t-HM PCI → coke rates 286 - 320 kg/t-HM
achieved in modern blast furnaces.
 Global average for PCI ≈125 kg/t-HM.
 PCI rate vs. Coke rate (Japan)
112
113

PCI quality requirements &

ancillary equipment
configuration
 PCI & BF combustion zone
114
 Summary: Challenges with high PCI Rates
116

 Raceway gas composition profile

 Burden distribution (Ore/coke)
 Accumulation of unburnt coal particles-deadman gas
permeability: How so?
 High RAFT- reduction of SiO2→↑[Si] pick-up
 Increase in solution loss reaction- high coke consumption:
How so?
 Slower dissolution rate of char in metal and slag: Why?
 Raceway collapse
 Alternative ironmaking processes
117
 Gas-based direct reduction- e.g. MIDREX®
118

Tanaka, H. (2015). Resources trend and use of direct reduced iron in steelmaking process. Kobelco Technology Review 33: 1-7
 Coal-based DRI (rotary hearth) technologies
119

Tanaka, H. (2015). Resources trend and use of direct reduced iron in steelmaking process. Kobelco Technology Review 33: 1-7
Conventional, direct & smelting reduction processe
120
 Smelting reduction: COREX process

121
 Ironmaking slags
122

 Formation of slag
 Role and properties of blast furnace slags
 Slag chemistry and basicity
 Slag viscosity
 Electrical conductivity
 Thermal conductivity

 Slag-metal reactions
 Sulphide capacity
123

Acidic

Basic

Ironmaking slags

Shaded zones of special importance in ironmaking: Composition of

basic and acid blast furnace slags.
Formation of slag (primary and final slag)
124
 Typical composition of blast furnace slags
125
 Slag Properties
 Blast furnace slags belong to the CaO-SiO2-Al2O3-MgO
126
system
 Composition is adjusted (through flux addition) to meet the
following criteria:
1. Liquidus temperature range 1350-1400oC (melting point
as low as possible).
2. Good fluidity and viscosity (viscosity as low as possible)
3. Capacity to retain impurities (S, K) by slag-metal or slag-
gas reactions
 Chemical composition is typically in the range
0.9<CaO/SiO2<1.3 (basicity); 9<% Al2O3<12; 5< %
MgO<10
 Complex physicochemical conditions affects formation and
behavior of slags: temperature at the reaction interface,
local oxygen potential, contact conditions between phases,
resulting from the size of the reacting zones and flow
conditions.
 Slag Properties

127
 Slag Properties


128
Molten slags are polymeric ionic melts. The cations (Ca2+,
Na+, Mg2+, Mn2+, Fe2+, etc.) are free and mobile whereas
anions (SiO44-, AlO45-, PO43-, etc.) are complex and less
mobile.
 Basic oxides help to break down the Si-O network (are
called network breakers). Acidic oxides are network
formers.
 Al2O3, Cr2O3, Fe2O3 behave as basic oxides at high
concentrations and as acidic oxides at low concentrations
(amphoteric in nature).
 The addition of basic oxides to the SiO2 melts results in
the progressive breakdown of the Si-O network
(implications on viscosity and fluidity?).
 Slag structure
129  Basic vs. acid oxides: Acid
oxides are network forming
oxides; Basic oxides are
network breaking oxides
 Similar oxides enhances each
other: increases chemical activity
 Different oxides weaken each
other: decreases chemical
activity; Lowering melting point

 Slag characteristics are determined by the ratio between

basic and acid oxides
 Slag Properties

130
 Slag structure
131
132

Slag atlas
 Effect on cations on degree of
polymerization
133

Polymerized silicate chains

Vs.
43% CaO, 35 % SiO2, 15
% Al2O3, 7 % MgO slag
SiO44- tetrahedron
AlO44- tetrahedron
Ca2+ cation

Mg2+ cation
 Slag Properties

134
 Slag viscosity (Poise or Pa.s)
135

 The viscosity of CaO-SiO2-Al2O3 slags should be as low as

possible→ preferably lower than 2 poise
 Viscous slags:
 Difficulties during slag-metal separation in the hearth
 Slowdown the rates of reaction of slag-metal-coke reactions
 Poor flow down from the bosh to the hearth → effect on the
cohesive zone (?)
 Hinder the upward flow of ascending gases through the burden →
permeability effect (?)
 Damage to the cohesive (melting and dripping)zone (??)
 Furnace tapping →temperature difference between viscous and
non-viscous (ideal) slags → viscous slags may solidify when the
temperature drops during tapping operation
 Slag-metal-gas reactions in BF

136 Kinetic considerations of slag-metal-gas reactions

 Impurities in blast furnace process

 Sulphur reactions in blast furnace

 Silicon reactions in the hearth

 Manganese reactions in the hearth

 Carburization reactions in the lower sections of the BF

 Impurities in blast furnace process
137
 Sulphur behavior: sources
138

 Input: 2.5-3.5kg/THM
 Coke and auxiliary fuels ( 80-90%), and rest from ferrous
burden and fluxes
 Sulphur transfer to hot metal
139
 Sulphur transfer from hot metal to slag
140
 Sulphide capacity
141
 Sulphur behavior
142

Fruehan (Ed.) (1998). The Shaping, Making, and Treating of Steel, Refining volume
 Impurities in blast furnace process
143
 Sulphur behavior: sources
144

 Input: 2.5-3.5kg/THM
 Coke and auxiliary fuels ( 80-90%), and rest from ferrous
burden and fluxes
 Why we de-S in BF and not in BOF
145

 Very little de-S takes place

during steelmaking. WHY?

 Ladle de-S usually using

strong agitation and CaO-rich
slag
Phosphorus behavior in the blast furnace
146
 Hot metal pre-treatment
147

Hot metal de-S before steelmaking by

injection of reactants such as CaC2, CaO,
MgO, Ca or Mg into the torpedo car

Hot metal de-P by use of injectants

containing CaO, CaF2, MgO, etc and
oxidizers (Fe2O3, O2, mill scale) into the
torpedo/transfer ladle; Dephosphorization
possible only if [%Si] < 0.2 %
 Hot metal treatment (cont.)
148
 Hot metal treatment (example)
149
 Behavior of circulating elements: Zinc
150

Trinkel et al. (2015). Behavior of Cr, Ni, Zn, Cd and Hg in

the Blast furnace-Critical Review of Literature Data and
Plant Investigations. Industrial & Engineering Chemistry
Research: 11759-11771
 Behavior of circulating elements: Pb
151

Trinkel et al. (2015). Behavior of Cr, Ni, Zn, Cd and Hg in the Blast furnace-Critical Review of Literature Data and
Plant Investigations. Industrial & Engineering Chemistry Research: 11759-11771
Behavior of circulating elements: Alkalis (K &Na)

152
Input: coke, PCI and ore in the form of oxides, silicates,
and carbonates
 Input rate: 1.5-5kg/THM
 Reduced to metal vapor in the lower part of the furnace
→ the vapor reacts with carbon and nitrogen to form
cyanides
 Detrimental to the strength of coke (+ catalytic effects)
and pellets→ reduces gas distribution and drainage of
liquids
 Promotes scaffold formation → decrease furnace
productivity and service life (+ corrosion of refractory
lining)
Behavior of circulating elements: Alkalis (K &Na)

153
Input: coke, PCI and ore in the form of oxides, silicates,
and carbonates
 Input rate: 1.5-5kg/THM
 Reduced to metal vapor in the lower part of the furnace
→ the vapor reacts with carbon and nitrogen to form
cyanides
 Detrimental to the strength of coke (+ catalytic effects)
and pellets→ reduces gas distribution and drainage of
liquids
 Promotes scaffold formation → decrease furnace
productivity and service life (+ corrosion of refractory
lining)
 Silicon behavior in blast furnace
154
 Silicon behavior in the blast furnace
155

Treatise on Process Metallurgy Volume 3

 Strategy for controlling the [Si]
 Decreasing the extent of SiO formation:
156
 Lowering ash in coke
 Lowering the RAFT
 Lowering the activity of SiO2 in coke and or PCI ash by CaO
injection through the tuyeres
 Decreasing the Si absorption by liquid metal by enhancing
the absorption of SiO2 by bosh slag:
 ↑ the bosh slag basicity
 ↓bosh slag viscosity → highly basic slags
 Removal of Si from metal by slag-metal reaction in the
hearth
 ↓hearth temperatures
 Optimizing slag basicity and viscosity
 Summary: Silicon and alkalis behavior
157

ISIJ (1987). Blast furnace phenomena and modelling

 Summary
158

 Slag properties (viscosity, basicity, fluidity)

 S flow in BF + de-S conditions
 P flow in BF
 Volatile- metal elements flow + process and
environmental challenges
 Alkalis flow + process and environmental challenges
 Si flow + process challenges
 Steelmaking processes
159Bessemer
Converter Open Hearth
Furnace

Steelmaking
Processes

Basic Oxygen Furnace Electric Arc Furnace

 Basic oxygen steelmaking processes
160

Hot metal from BF

BOF Steelmaking
 Basic oxygen furnace process
Pure oxygen injected into steel at
161 supersonic speed (~3Nm3 of O2 per
ton of steel per min)
 FeO formed by reaction of O2 with
steel bath
 FeO reacts further → fixes oxygen
activity in steel
 Kinetics critical, especially for
decarburization
 Blowing time: 15mins
BOF inputs
Hot metal~1350°C, Fe-4.5%C,
0.5%Si, 0.1%Mn, 0.15% P, 0.01%S To slag (CaO/SiO2≈2.5;
Fluxes: (CaO, MgO) 10% MgO, 25% FeO)
Scrap
Oxygen
 Combined blowing in BOF operation
162
LD/BOF equipped with postcombustion nozzles
163
Oxygen
Oxygen
lance
Zone of post
combustion

Orifices

Emulsion Oxygen
jets
Slag

Iron
Lance with post
droplets
combustion nozzles
above the lance tip
a) LD/BOF with Iron b) Lance equipped with
conventional lance bath
postcombustion nozzles
 Oxygen lance and blowing practice
 Design and blowing program→ effect of blow velocity and lance
164
height on oxygen converting efficiency
 Rate and oxidation order of iron melt constituents,
 Formation of iron droplets and their emulsification in the slag,
 Slag foaming,
 Splashing and sculling phenomena
 Lance tip and nozzle design→ maximizing the control over the blow
and extending the lance life
 Formation and stability of slag foam during blow→ dependent on
oxygen jets from the lance
 Lance design + blowing rate + height of immersion→ refining of
iron melt + postcombustion degree (CO → CO2)+ refractory lining
wear
 Low lance height → ↑mixing intensity in the iron bath and the
transport rate of minor elements to the surface zone of the melt →
↑rate of oxidation
 Interaction of gas jet with steel bath
Li et al. (2016).Determination of cavity
dimensions induced by impingement of gas
Jet momentum and penetration depth
165
jets onto a liquid bath. Metallurgical 𝑀 𝜋ℎ0 ℎ0 2
Transaction 27 B 2016: 116-126 = (1 + )
𝜌1 𝑔𝐻3 2𝐾 2 𝐻 𝐻
 Mass balance in BOF operation
166
 Mass balance in BOF operation
167
 BOF control philosophy
168
 Basic oxygen steelmaking reactions
 When oxygen first contacts in liquid iron-carbon alloy, it
169
initially reacts with iron → due to the relative abundance of
the iron in comparison to carbon.
[Fe]bath + 0.5O2(g) → (FeO)slag
[Fe]bath + [O]bath → (FeO)slag
 Decarburization reactions:

[C]bath + 0.5O2(g) → (CO)gas

[C]steel + [O]steel → (CO)gas
 Slag metal reaction:

(FeO)slag + [C]bath → [Fe]bath + (CO)gas

 At high carbon content the rate of mass transfer is high →
most of the FeO formed is reduced. Rate of decarburization
is controlled by the rate of oxygen supply to tye reaction
interface.
 Oxidation reactions
170
Oxidation Process Chemical Reactions By-product

Decarburization reactions [C] + [O] ↔ CO(gas) Off gas

2[C] + O2(gas) ↔ 2CO (gas)

[CO] + [O] ↔ CO2(gas)

Oxidation of impurities from steel [Si] + 2[O] + 2[CaO] ↔(2CaO •SiO2) Slag
(FeO) + [C] = [Fe] + CO
[Mn] + [O] ↔ (MnO)

2[P] + 5[O] + 3(CaO) ↔ (3CaO•P2O5)

 Oxidation of impurities
171
Phosphorus behavior in BOF:
174

 Oxidation reaction: 2[P] + 5[O] = (P2O5)

Ionic: [P]+ 2.5[O] + 1.5(O2-)→(PO43-)
 Strongly exothermic reaction. De-P
aPO3
K  4
3
favored by high FeO (oxidizing
a 
5
hP   hO  2
O 2
2 conditions), basic slag & low
temperature.
Phosphorus control
 Equilibrium: Temperature; Slag composition (mainly basicity, % FeO);
Slag volume
 Kinetics: Stirring →Bottom stirring/post stirring; Lime dissolution
→early dissolution of CaO (initial soft blowing); Slag not
supersaturated with CaO and MgO
 Plant practice: reduced slag carry-over from steelmaking vessel to
 Dephosphorization of steel
175

 Metal-slag reaction → Partition coefficient L (dependent on

equilibrium and kinetics)
𝑤𝑡. % 𝑋
𝐿𝑒𝑞 =
𝑤𝑡. % 𝑋
Where (wt. % X): concentration of element in slag
[wt. % X]: concentration of element in metal
 Concentration in metal after reaction:
[% X ]0
Element total in metal & slag,
[% X ]  as a % of metal
W 
1  Leq  slag
 Wsteel 


 Given that Wslag/Wsteel = 0.12 in steelmaking, and Lp = 100 for

dephosphorization. Calculate the tap phosphorus relative to the initial
phosphorus concentration
Phosphorus behavior : Control of de-P
176

 Equilibrium and mass balance effects:

 Lower tapping temperature (feasible if ladle reheating
furnace and/or chemical heating is available).
 ↓Slag volume→ controlled by [%Si] in hot metal
 Higher slag basicity
 Limit slag carry-over to ladles.
 Kinetic effects
 Early dissolution of CaO (initial soft blowing)
 Slag not supersaturated with CaO and MgO
 Bottom stirring (mixing effects)
 Electric furnace steelmaking
177

Hot metal from BF

BOF Steelmaking
 Electric arc furnace
178
 Feed materials (scrap, fluxes,
carbon) charged through the top of
the furnace (roof opened).
 Arc struck to melt down scrap
 Some materials can be fed
continuously (e.g. DRI, oxygen, coal).
 Reactions similar to BOF but with
much less C removal
 Slag similar to BOF (i.e. highly basic)
Typical input materials to EAF
To slag: CaO/SiO2=2.3,
DRI: 85% Fe, 7% FeO, 2% SiO2, 0.5%
11%MgO, 29%FeO
Al2O3, 0.06% P2O5, 0.7%CaO, 4%C
Fluxes: (CaO, MgO)
Oxygen To produce CO→ slag foaming
and nitrogen removal
 Typical EAF mass balance
179  Feed materials: Solid DRI,
scrap, carbon, oxygen, fluxes
 Energy sources: Electrical
energy, combustion
 Electrical control: power input,
arc length
 Oxy-fuel injection (lances
(above) or tuyeres (below) the
steel level
 Slag foaming to cover arcs →
energy efficiency
 Slag composition highly basic
(CaO/SiO2≈2.3)
180
 EAF slag foaming practice

181 Definition

 Benefits
 To decrease radiative losses from arc & decrease nitrogen pick-up
in steel
 Arc efficiency can increase to 60-90% with foaming slag (vs. ~40%
without)
 Can use longer arc length (higher arc voltage; higher power factor)
 Requirements
 Gas generation (carbon and oxygen injection or C + FeO in feed)
 Correct slag composition (basicity, FeO, solids): foaming index is
foam height divided by gas flow rate per unit area
182
 Developments in the EAF: Specific energy consumption
183
 Steel refining
184

Hot metal from BF

BOF Steelmaking
 Steel refining: Control of product quality
185

 Variables: P, temperature, C
 Control philosophy:
 Highly basic slags (for P-removal)
 Mass and energy balance for temperature (scrap cooling
vs. energy sources-Si, Fe, C oxidation)
 Slag composition controlled to approach CaO and MgO
saturation
 Reactions approach equilibrium (-except P)
 Task
186

 A Basic Oxygen Furnace is treating 100 tons of pig iron, with

composition 4 wt. % C, 1.5 wt. % Si, 0.5 wt. Mn, and Fe constituting
the rest of bath composition, by injecting pure oxygen gas.
1) With the aid of a clearly labelled sketch and equations, discuss
the phenomena taking place at the slag-metal-gas interface in
oxygen steelmaking process
2) If all the impurities are removed and in addition 2.5 tons of iron is
oxidized, how many kilograms (kgs) of oxygen gas are required?
Assume half of the carbon is oxidized to CO and half to CO2.
3) Calculate the composition of slag in wt. %, assuming all the FeO,
MnO and SiO2 report to the slag phase.
Atomic weights: Fe = 55.845; C =12.01; O =16; Mn =54.938; Si =
28.086; R=8.3145Jmol-1K-1
 Stainless steel refining
187

 Composition: <0.1% C (as low as 0.005% C for ultra-low

carbon s.s.), 12-18% Cr
 Sources of chromium: ferrochromium alloys (HCFeCr,
MCFeCr, LCFeCr)
 HCFeCr typical composition: 51% Cr, 6-7% C, balance Fe
 Crude stainless steel~2%C
 Excess C removed by oxygen blowing (diluted with Ar or
N2)
Typical composition of some stainless steels grades
188
 Stainless steel refining
189

 Unit processes
 Slag-metal reactions
 Decarburization reactions
 Equilibrium considerations
 Ladle metallurgy
 Deoxidation reactions
 Control of non-metallic inclusions
 Stainless steel refining
190

The Steelmaking Processes for Stainless Production (a) AOD (b) RH-OB/KTB (c)
VOD (d) AOD-VCR (e) K-BOP/K-OBM-S (f) CLU (g) ASM/MRP Side or Bottom
Blow Plug or Tuyeres
Conventional processes for austenitic stainless
steels
191
 Argon-Oxygen Decarburization (AOD)
192
 Decarburization reactions

193
Oxidation of dissolved carbon:
2[𝐶]in 𝐹𝑒 + 𝑂2 𝑔 = 2𝐶𝑂(𝑔)
 Injected oxygen first reacts with chromium:
2[Cr]in Fe + 1.5O2 (g)→ <Cr2O3>solid
 Solid Cr-oxide further reacts with dissolved carbon:
(Cr2O3)in slag + 3[C]in Fe → 2[Cr]in Fe + 3(CO)g;
 (aCr ) 2 ( pCO )3  88704 
 P  a 
3
CO
2
Cr
ln K  ln     56.67 K
 C
( a ) 3
 a

Cr 2 O 3  T a  f  %C 
Cr2 O3 C
3 3

 Carbon removal (as opposed to Cr-loss to slag) is favored

by:
 High temperatures (1700°C)

 Lowering p(CO) (by dilution and/or vacuum)

Reduction Stage: Reduction of Cr from Slags
194
195
 Modelling and process control
196

Zonal description of the AOD

system
 Molten metal with dissolved
elements such as C, Si, Mn, Cr,
Ni and N
 Slag, which can be molten or
solid, containing oxides such
as CaO, Al2O3, SiO2, MnO,
MgO, Cr2O3, and FeO
 Inert gas and oxygen which
reacts to form CO
 Modelling and process control
197
 Modelling and process control
198

(Cr2O3)in slag + 3[C]in Fe → 2[Cr]in Fe + 3(CO)g

 Modelling and process control
199
 Summary 1: Decarburization of stainless steels


200 Considering only the dissolved carbon and chromium, the
following reaction occurs during the addition of oxygen:
1
C + 𝑂2 = 𝐶𝑂(𝑔)
2
 The following unwanted reaction may also take place:
3
2 𝐶𝑟 + 𝑂2 = 𝐶𝑟2 𝑂3 (𝑖𝑛 𝑠𝑙𝑎𝑔)
2
 Overall decarburization reaction via slag phase
(𝑎𝐶𝑟 )2 (𝑝𝐶𝑂 )3 −88704
𝑙𝑛 𝐾 = 𝑙𝑛 3
= + 56.67
(𝑎𝐶 ) 𝑎𝐶𝑟2𝑂3 𝑇
𝐶𝑟2 𝑂3 (𝑠𝑙𝑎𝑔) + 3 𝐶 = 2 𝐶𝑟 + 3𝐶𝑂(𝑔)
 𝑝𝐶𝑂
Calculate the equilibrium ratio K = for the decarburization involving
𝑎𝐶0
the
201
slag phase
𝐶𝑟2 𝑂3 (𝑠𝑙𝑎𝑔) + 3 𝐶 = 2 𝐶𝑟 + 3𝐶𝑂(𝑔)

(𝑎𝐶𝑟 )2 (𝑝𝐶𝑂 )3 −88704

𝑙𝑛 𝐾 = 𝑙𝑛 = + 56.67
(𝑎𝐶 )3 𝑎𝐶𝑟2𝑂3 𝑇

Reaction ΔG0 (J/mol)

1 -114 400 – 85.77T

𝑂 + 𝐶 = CO(𝑔)
2 2(𝑔)
[𝐶] = 𝐶 22 590 + 4226T
3
𝑂 + 2[𝐶𝑟] = 𝐶𝑟2 𝑂3(𝑠𝑙𝑎𝑔) . -1 110 000 + 247.0T
2 2(𝑔)

2[𝐶𝑟] = 2𝐶𝑟 -38 500 + 93.7

 Summary 2: Eqm considerations
 Control techniques to minimize chromium oxidation:
1) Controlling the temperature to manipulate the equilibrium
carbon content,
2) Dilution, particularly in the argon-oxygen decarburization
process, where inert gases such as nitrogen or argon are
injected to lower the partial pressure of CO in the bath and
hence allow higher chromium content to be in equilibrium with
lower carbon content,
3) Vacuum refining to remove the CO and force the equilibrium
of equation (Cr2O3)in slag + 3[C]in Fe → 2[Cr]in Fe + 3(CO)g to
the left, and
4) Careful manipulation of slag chemistry (highly basic slags).
 Ladle metallurgy/ secondary steelmaking

203
Processing step after BOF, AOD and/or EAF steelmaking (steel
at tap contains ~0.05% C, 0.06% O). Produce steel grades
with narrow tolerances in chemistry and consistency.
 Deoxidation →adding Al, Si-Mn, C to remove dissolved O
 Homogenization and superheat adjustment → chemical
composition and temperature of liquid steel before casting.
 Alloying → ferro alloys and carbon additions.
 Vacuum degassing – Removal of hydrogen and nitrogen
 Decarburization – Removal of carbon for meeting the
requirement of certain grades of steel.
 Desulfurization – Reduction of sulfur concentrations as low as
0.002%
 Steel cleanliness removal of non-metallic inclusions
 Ladle metallurgy/ secondary steelmaking
204

Courtesy of JFE Steel Ltd

 Deoxidation treatment of stainless steels
205
 Deoxidation treatment of stainless steel
206
 Deoxidation treatment of stainless steel
207

Deoxidation with Si/Mn

Deoxidation with Al
Ladle desulphurization of Al-Killed steels
208
 Ladle furnace desulphurization
209

 Desulphurization reaction → Al-killed steels

Source of non-
3[S] + 3(CaO) + 2[Al]=3(CaS) + (Al2O3)
metallic inclusions
 Requirements:
 Basic slags, reducing conditions
 Uses CaO-rich slag
 Composition and origin of slag
 ~10% SiO2 → carry-over from steelmaking)
 ~10% MgO → added to protected slagline
 ~55% CaO → added to increase basicity
 ~25% Al2O3 → deoxidation product+ added
 Slag mass typically 10kg/ton steel
 Ladle furnace desulphurization: Reactions
210
211
 Ladle metallurgy-Unit processes
1. Ladle Degassing (VD, Tank Degassing)
212  Ladle with molten steel is
placed into a vacuum
chamber.
 Porous refractory plug in the
ladle bottom →argon is
supplied during vacuum
treatment.
 De-S slags (high S-affinity)
 Ar & CO favor the flotation of
nitride and oxide inclusions
and removal of gaseous
Source: nitrogen.
http://www.substech.com/dokuwiki/doku.php
?id=ladle_refining
 2. Vacuum oxygen decarburization (VOD)
 VD, Tank Degassing chamber is
213
equipped with a vertical water
cooled lance for blowing oxygen
on the molten steel surface.
 Benefits of ladle furnace:
 Deep carbon removal and ability to
decarburize the steel with minor
chromium losses
 Degassing (H &N removal)
 Sulfur removal
 Precise alloying control
 Removal of non-metallic inclusions
(oxides and nitrides)
 Temperature and chemical
homogenization.
Source: http://www.substech.com/dokuwiki/doku.php?id=ladle_refining
 3. Recirculation degassing (RH, RH-OB)
 Vacuum chamber having two
214
snorkels connected to the chamber
bottom.
 Benefits of ladle furnace:
 Degassing (H & N removal)
 Oxygen removal
 Carbon removal
 Sulfur removal
 Precise alloying
 Removal of non-metallic inclusions
removal
 Temperature and chemical
homogenization.
 Phosphorus removal (RH-OB)
Source: http://www.substech.com/dokuwiki/doku.php?id=ladle_refining
 Reactor design → refining
215

 Refining metallurgy→ removal of impurities and inclusions

from molten metal

Sources on impurities:
1. Raw materials (ores) used in the
extraction process, e.g. P, S
2. Enter the melt during alloying and
refining treatment, e.g. non metallic
inclusions from deoxidation process
3. Impurity pick up from refractories,
atmosphere and slag
 Reactor design → refining
 Heterogeneous reactions → slag-metal-gas-refractories
216 reactions in ladle refining
 Thermodynamics of degassing
217

 Decarburization, nitrogen and hydrogen removal

[𝐻]𝑠𝑡𝑒𝑒𝑙 +[𝐻]𝑠𝑡𝑒𝑒𝑙 = 𝐻2(𝑔)

[𝑁]𝑠𝑡𝑒𝑒𝑙 +[𝑁]𝑠𝑡𝑒𝑒𝑙 = 𝑁2(𝑔)

[𝐶]𝑠𝑡𝑒𝑒𝑙 +[𝑂]𝑠𝑡𝑒𝑒𝑙 = 𝐶𝑂(𝑔)

 Steelmaking slags and clean steel production
218

 Role and properties of slags

 Clean steel-removal of inclusions
 Clean steel summary
 Mould fluxes
 Continuous casting
 Role and properties of steelmaking slags
219
(1) Control of liquid metal bath
chemistry through controlled slag-
metal-gas reactions,
(2) Insulate the liquid metal bath from
atmospheric reactions such as re-
oxidation and nitrogen pick-up
(3) Refining role to remove impurities
such as sulphur, phosphorus and
inclusions from the liquid metal
bath,
4) Thermal insulation on the liquid metal bath to prevent heat losses,
and,
5) Slag bath protects the furnace refractory lining from coming into
direct contact with the liquid metal bath hence, thereby reducing the
metal bath contamination through refractory-metal interactions
Clean steel production: Sources of impurities
Impurity
220 Main source Removal
C Hot metal, scrap, alloys Steelmaking; degassing
H Water leaks, raw materials, air, Degassing
slag
N Raw materials, air, stirring gas Steelmaking; degassing
(BOF), alloys
O Steelmaking, air, reducible oxides [O]dissolved: deoxidizers
in slag, alloys Obound (inclusions): flotation
P Hot metal (ore), scrap, alloys, HM de-P; steelmaking
reductant

S Hot metal (ore+ coke), scrap, coal BF ironmaking; HM de-S;

ladle desulphurization
 Origins of non-metallic inclusions
222

Sahai, Y. and Emi, T. (2008). Tundish Technology for Clean Steel Production. World Scientific
Publishing, Singapore
Origins of exogenous non-metallic inclusions
223

Sahai, Y. and Emi, T. (2008). Tundish Technology for Clean Steel Production. World Scientific Publishing,
Singapore
Origins of indigenous non-metallic inclusions
224

 Indigenous non-metallic inclusions occur as a result of

deoxidation reaction
n[M] + m[O]= 𝑀𝑛 𝑂𝑛
where M is the deoxidizing element (e.g. Mn, Si or Al) dissolved
in the steel melt

 Nucleation and growth of the resulting oxides MnOm (→MnO,

SiO2, MnO-SiO2 or Al2O3) to form liquid globular inclusions,
irregular solid inclusions, and/or clusters of solid inclusions.
 Removal of non-metallic inclusions
 Inclusions absorption by slag → mechanistic steps
225
1) Flotation in the bath → transport of the inclusions to the steel-
slag interface
 Stokes law: differences between densities of non-metallic
inclusions and molten steel
 Electromagnetic stirring and argon injection to improve the
removal of inclusions
2) Movement of inclusions to the interface and breaking the
surface tension of steel → Marangoni effect
3) Dissolution in slag → removal from the steel-slag interface for
full incorporation into slag
 Ca-treatment (in the form of Ca-Si) → modify unmelted Ca-Mg
spinels into calcium aluminates and CaS with low melting point
 Optimized slag properties → ↑solubility into, and entrapment
and absorption of non-metallic inclusions by slag
 Clean steel production: Processes
226

 Available processes:
 Deoxidation
 Slag control (↓ slag volume and carry-over slag)
 Gas stirring → eye formation
 desulphurization→ hot metal and ladle
 Inclusion modification→ Injectants and slag-based
strategies
 Vacuum degassing
 Casting→ tundish, mold
 Inclusion control by Ca treatment
227
228

Clean steel
production: Summary
 Task
1)
229 The rule of thumb in pyrometallurgical processes is based on the

statement: “Slag engineering is everything. Take care of the slag

and the furnace takes care of itself.” Using a refining process of
your own choice, discuss this statement.
2) With reference to any stainless steelmaking unit process of your
choice, discuss the role and properties of slags in controlling
product quality.
3) Why is the process of slag formation in steel refining unit
operations critical? Discuss any three possible ways of
accelerating the process of slag formation in steelmaking
4) With reference to possible limiting steps, discuss the kinetics of the
decarburization process in stainless steelmaking. What measures
must be employed to intensify the decarburization process?
5) Discuss on the effects of surface tension on inclusion control
Continuous casting and solidification process
230
 Mold fluxes
231
 Composition range of mold fluxes
232
 Mold fluxes
233

Functions and properties of mold fluxes

 Manufacturing and fabrication
234
 RECAP
 Raw materials engineering (coke, sinter, pellets)
235 Blast operation and furnace functional zones

 Operational and control philosophy
 Slag engineering (functions, properties, control)
 Oxygen steelmaking
 Operational and control philosophy
 Slag engineering (functions, properties, control)
 Stainless steel refining
 Operational and control philosophy
 Slag engineering (functions, properties, control)
 Slag-metal reactions (decarburization)
 Deoxidation
 Clean steel strategies
 Slag engineering (functions, properties, control)
 Inclusions control
 Environmental, social and sustainability aspects in iron and steel
industry
236 Any questions so far?
 Bulk ferroalloys
237

 Major additives in steelmaking

 High carbon ferrochromium alloys

 Ferromanganese alloys

 Ferrosilicon alloys
 Bulk ferroalloys-typical functions
Elemen Influence on Influence on Typical applications in steels
t structure properties
Mn
238 Austenite Increase Alloying element in low alloyed steels
forming, hardenability, containing up to 1.6 wt. % Mn;
substitutional strength, toughness, Hadfield steel 13 wt.% Mn; AISI* 200
atom, carbide hot workability series stainless steel contains 5-10
stabilizer wt.% Mn
Cr Ferrite forming, Increases Low-alloyed steels contain up to 2 wt.
substitutional hardenability, % Cr; stainless steels typically contain
atom, forms strength and corrosion 10.5-25 wt. % Cr; widespread
carbides resistivity applications in heat resistant and tool
steels
Ni Austenite Increases strength, Case hardening steels contain up to
forming, toughness, impact and 3.5 wt. % Ni; stainless steels typically
substitutional corrosion resistance contain8-20 wt. % Ni; heat-resistant
atom steels contain up to 25 wt. % Ni
Si Ferrite forming, Ferrite hardening Deoxidation; slag reduction; spring
substitutional steels typically contain 1.7-2.2 wt. %
atom Si; Electrical Si steels contain 1-4 wt.
% Si
 Submerged arc furnace vs. blast furnace
239

 Manganese ferroalloys are commercially produced from the

carbothermic reduction of manganese ores, either in the blast
furnace or in electric furnaces ferroalloys

SAF Blast Furnace

Energy source Electric C-consumption (coke)

C-consumption 350kg/t alloy 2000kg/t alloy

Alloy FeMn/SiMn FeMn

World capacity > 90% < 10%

 Production of HCFeMn: Main goals
240
1. To operate on a stable high load- Carbon balance, Fines, Zn
content, water

2. Minimize energy consumption- Raw material mix, Boudouard

reaction, Metal chemistry

3. Produce metal and slag of required composition

4. Metal chemistry and yield –High Mn yield

5. Minimize emissions of CO2 and noxious compounds and

gases- Raw material mix, Off-gas cleaning systems , Furnace
operation
 Submerged arc furnace
241
 Effects of ore properties
1) Product quality
242
 Ore Mn/Fe ratio: main determinant of Mn/Fe in alloy

 Level of contaminants in alloy, e.g. P, Ti, and B, is affected by their

concentration in ore and other raw materials

2) Energy consumption: High oxygen content and high CO-reactivity
of ore will decrease the energy consumption. Why?
3) Furnace performance
 Raw materials with low strength results generates high amounts of

fines and results in unstable furnace operation

 Chemical composition of ore affects slag composition and amount of

fluxes needed, and hence the total slag volume

 Ore properties and mineralogy affect temperature and conditions

at the top of the coke bed and the reduction of SiO2 and MnO, and
hence, the Si and MnO contents in the final slag
243

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Slag strategy in FeMn production
 Distinct processes for manganese ferroalloys by their slag
244
chemistry and operating temperature regimes:
1) HCFeMn production using discard slag in the temperature
range 1400-1450°C,
2) SiMn production utilizing only ore as source of manganese in
the temperature range 1500-1600°C
3) HCFeMn production using a rich slag practice and the
subsequent production of SiMn (commonly referred to as the
duplex process) in the temperature range 1400-1450°C

 In the HCFeMn-SiMn duplex process, the tapped slag contains

about 30 to 50 wt. % MnO, which is normally reprocessed for
the production of silicomanganese or manganese metal
 Duplex process
1) HC-FeMn-Discard slag
245
practice
 XXXX % in slag. The slag is
a low value byproduct and
goes to land fill
2) Duplex operation –Low
slag basicity
 35-50% MnO in HC –FeMn
slag. The slag from HC-
FeMn process is used as raw
material for the SiMn
process
3) SiMn –Ore charge
 Higher P content in metal

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Reaction zones in the SAF
246
 Furnace operation and control systems
247 Furnace power control: Maximum load

 Electrode position control: fixed resistance

 Metallurgical control: charge composition

 The energy dissipation is highest between electrode tip and

the metal bath. The temperature rises continuously from the
top of the furnace to the coke bed.

 The mass transport of charge and gas (counter-current) is

highest close to the electrode and slowest far from the
electrode.
Carbon materials in FeMn/SiMn production
248

1. Composition
 Fixed carbon
 Ash content
2. CO2 Reactivity
 Type of carbon (source)
 Alkalis present (K)
3. Slag reactivity
 Reactivity
 Slag flow
 Size
4. Electrical resistance
Carbon type
Size/strength Ringdalen, E. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek
 Coke bed in SAF
249

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Coke bed in SAF processing of FeMn
250

Sketch of a 75 MVA HCFeMn furnace cut through one electrode (Barcza et al. 1979).
 Coke bed in SAF
251
 Flow of slag in coke bed (FeMn)
252

Tangstad, M. (2016). The 2nd SAIMM School of Ferromanganese Production, Mintek

 Ferroalloy slags (fundamentals-recap)
253

 Slag structure
 Chemical activity
 Slag composition
 Slag viscosity
 Electrical resistivity
 Slag structure
254  Basic vs. acid oxides: Acid
oxides are network forming
oxides; Basic oxides are
network breaking oxides
 Similar oxides enhances each
other: increases chemical activity
 Different oxides weaken each
other: decreases chemical
activity; Lowering melting point

 Slag characteristics are determined by the ratio between

basic and acid oxides
 Slag structure
255
256 Questions?