Professional Documents
Culture Documents
Pengantar Metalurgi Ekstraktif
Pengantar Metalurgi Ekstraktif
MetE 208
Chemical Principles of Materials Production
Prof.Dr. Yavuz A. TOPKAYA
1. INTRODUCTION
1.1 Sources of Metals
1.2 Mineral Dressing
1.3 Preliminary Treatment
1.4 Extraction Processes
1.5 Fuels and Refractories
1.6 Ironmaking
Flowsheet
Blast Furnace Charges and Operation
1.7 Steelmaking
Flowsheet
Steelmaking Processes
1.8 Non-ferrous Metals
1.8.1 Copper Production (As flowsheets)
1.8.2 Zinc Production (As a flowsheet)
1.8.3 Lead Production (As a flowsheet)
1.8.4 Aluminum Production (As a flowsheet)
Conservation of Mass
Mass Relations in Metallurgical Reactions
Volume Relations in Metallurgical Reactions
The gram-atom, kg-atom, gram-mole, kg-mole
Gas Laws
Excess of Reactants
2.4 Examples
2.4.1.
2.4.2.
2.4.3.
2.4.4.
2.4.5.
Combustion
Excess Reactants
Roasting
Gas Treatment
Problem Hours on Material Balances
3. HEAT BALANCE
3.1 Kinds of Energy and Conservation of Energy
3.2 Heat Balance
3.3 Procedure in Calculating a Heat Balance
3.4 Choice of Reactions
3.5 Examples of Heat Balance
4. REFERENCES
4.1
4.2
4.3
4.4
4.5
4.6
4.7
5. MARKING
1st Mid-Term
25 %
2nd Mid-Term
25 %
Final
40 %
Homeworks
10 %
CHAPTER 1
1.1. THE SOURCES OF METALS
Metallurgy is the science and art of extracting metals from their ores, refining them
and preparing them for use.
Ores are naturally occurring deposits in the Earths crust. The ores are mined and
treated by various unit operations (mechanical processes) and unit processes (chemical
metallurgical processes) to extract metals, and to convert them into the metallic (chemically
uncombined) form.
Earths crust refers to the outer siliceous shell of the Earth which is about 35 km thick.
Metallic ores and other mineral products are produced from this crust. Therefore, the original
source of all metals is the Earths crust.
Average analysis of the Earths crust is given in Table 1. As it can be seen from the
table that oxygen, silicon, aluminum and iron are the four most abundant elements.
Since engineering metals Al, Fe, Mg and Ti are far more abundant than the other
metals. There is never likely shortage of these due to exhaustion of the ore deposits.
The commonly known metals, e.g. Au, Pb, Sn are so small in quantities in the Earths
crust that their commercial recovery is impossible. But, by natural events, those are
concentrated in certain parts of the Earths crust resulting in their economical recovery.
Ore deposits are metal-bearing veins, beds, placer deposits and solutions, which are
used to extract, metal commercially. Geological processes result in the concentration of
metals in ore deposits.
Table 1
Composition of the Earths Crust
Element
%
Element
Element
O
Si
Al
Fe
Ca
Na
K
Mg
-
46.66
27.72
8.13
5.00
3.63
2.89
2.59
2.09
-
Ti
H
Mn
P
F
S
Cl
C
Rb
Ba
Zr
Cr
Sr
V
Ni
Cu
0.44
0.13
0.10
0.08
0.08
0.052
0.048
0.032
0.031
0.025
0.022
0.020
0.015
0.015
0.010
0.010
Zn
W
Li
Ce
Sn
Y
Nb
Nd
Co
La
Pb
Cf
Th
-
0.0080
0.0069
0.0065
0.0046
0.0040
0.0028
0.0024
0.0024
0.0023
0.0018
0.0016
0.0015
0.0011
-
TOTAL
98.65
TOTAL
1.110
TOTAL
0.0459
Less than 0.001 % (Cs, Ge, Be, As, U, Mo, Ta, Sb, etc.)
Less than 0.0001 % (Hg, Tl, Bi, Cd, Ag, In, Se, Pd, Pt, Au, etc)
3
Copper ores
Most important ore minerals of copper are chalcopyrite (CuFeS2), bornite (Cu5FeS4),
chalcocite (Cu2S), covellite (CuS), enargite (CuAsS4), malachite (CuCO3.Cu(OH)2), cuprite
(Cu2O) and chrysocolla (CuSiO3.2H2O).
Ores: The primary ore mineral in copper ores is chalcopyrite. Others are secondary
minerals formed by the alteration of primary chalcopyrite and chalcocite. Sulfide ores in
nature are usually associated with pyrite (FeS2) or pyrrhotite (Fe1-xS) and other base metal
sulfides such as ZnS, PbS, NiS, etc. The ore minerals are usually associated with siliceous and
other gangue minerals. Therefore, the grade of ore is reduced to 1 2 % Cu.
Lead ores
The only important lead ore mineral is galena (PbS). Anglesite (PbSO4) and cerussite
(PbCO3) are found in the upper portions of some lead ore deposits but they are not important
commercially.
Most lead ores are found as veins, so are not suited to bulk mining methods. As a
result, the average grade of lead ore mined is higher than that of copper ore; in the range 3.0
to 8.0 % Pb and associated with zinc and silver.
Zinc ores
Sphalerite (ZnS) is the only important zinc mineral and usually associated with PbS or
CuFeS2 and cadmium. Smithsonite (ZnCO3) and calamine (Zn2(OH)2.SiO3) often occur in the
oxidized portions of sphalerite ore bodies. Grade of zinc sulfide ores: 2 12 % Zn.
The precious metal ores
Gold, silver and platinum metals most commonly occur as native metals. They are in
the metallic state but they are usually alloys rather than pure metals. In a few cases, gold
occurs as calaverite (AuTe2). Besides native silver, other important ore minerals of silver are
argentite (Ag2S), pyrargyrite (Ag3SbS3), etc.
Gold, silver and platinum are usually associated with base-metal sulfides and pyrite.
Chromium ores
The economical mineral in chromium ore is chromite (FeO.Cr2O3). Commercial
chromium ores usually contain 40 % Cr2O3 or more.
i.
ii.
Crushers
(+) Oversize
Screens
(-) Undersize
Grinding
(+) Oversize
Classification
(-) Undersize
Concentration
Concentrate
Tailing
diagonal of each screen opening is equal to the edge of the previous screen. So, the linear
dimension of each opening differs by a constant factor of 2 = 1.414.
Tyler screen scale starts with 1.05 inch (26.67 mm), for smaller particle sizes the
dimensions are usually given in microns (1 micron = 10-3 mm). Thus, 200 mesh (#) is equal to
74 microns in the Tyler Screen Series, Table 2.
The result of a screen analysis is given as the fraction of the sample which passes
through one screen but which is stopped by the subsequent screen so we can say that a certain
percentage is + 26.67 mm (coarser than the coarsest screen), another percentage is 20 mesh
+ 28 mesh (dimensions between 0.833 mm and 0.589 mm) and finally that a certain
percentage is 200 mesh (finer than 0.074 mm or 74 microns). The mesh number does not
directly indicate the size of the aperture, and the aperture can be calculated from the mesh
number if the wire diameter is known.
1 inch (25.4 mm) = Number of wires * Wire diameter + Number of apertures * Aperture size
Table 2
2 series
Tyler Mesh #
3
4
6
8
10
14
20
28
35
48
65
100
150
200
270
400
Feed
Fluid Velocity, V
Spigot Product
(particles with terminal velocities > V)
1.2.3. Concentration
The second fundamental (main) operation in mineral processing, after the release, or
liberation, of the valuable minerals from the gangue minerals, is the separation of these values
from the gangue, i.e. concentration.
Concentration is usually accomplished by utilizing some specific difference in
physical (or chemical) properties of the metal and gangue compound in the ore.
In concentration the following terms are used:
Head is the feed to a concentrating system.
Concentrate is defined as the valuable mineral(s) separated from ore undergoing a
specific treatment.
Tailing is the fraction of ore rejected in a separating process. It is usually the valueless
portion, i.e. discard or waste.
Middlings are the particles of locked valuable mineral and gangue, i.e. liberation has
not been attained. Further liberation can be achieved by further comminution.
Recovery is the percentage of the total metal, contained in the ore that is recovered in
the concentrate.
Physical Concentration Methods
1. Separation dependent on optical and radioactive properties of minerals, i.e.
hand pickling, optical sorting, radioactive sorting, etc.
2. Separation dependent on specific gravity (density) difference of minerals, i.e.
heavy-media separation, gravity concentration by use of tables, jigs, cones, etc.
3. Separation utilizing the different surface properties (i.e. surface chemistry) of
the minerals, i.e. froth flotation, etc.
4. Separation dependent on magnetic properties of the minerals, i.e. low and high,
dry and wet magnetic separation, etc.
5. Separation dependent on electrical conductivity properties of the minerals, i.e.
electrostatic separation, etc.
So mineral processing is concerned mainly with the physical methods of separation of
minerals. Pyrometallurgy and hydrometallurgy may also deal with raw materials but those
processes change the character of some or all of the constituents of the raw materials.
10
1.3.2. Calcination
Calcination is the thermal treatment of an ore or a concentrate to effect its
decomposition and the elimination of a volatile product, usually CO2, water vapor, or other
gases.
Therefore, by contrast with drying, calcination involves the removal of H2O, CO2, etc.,
which are chemically bound as e.g. hydrates or carbonates.
Lost
Material
Free water
Drying
Lost
Chemically bound H2O,CO2
Completely dehydrated
and calcined material
Calcination
Increasing Temperature
T 900o C
iii.
1.3.2.1.Calcination Furnaces
Shaft furnace For the calcination of coarse limestone
Rotary kiln For the calcination of materials with mixed particle size or lumps which
disintegrate during the process
Fluidized bed For materials of uniform, small particle size
Fuels used in calcination furnaces are gas, oil, coke, pulverized coal, etc.
Temperature of gas and solids during calcination of limestone in a coke-fired shaft furnace,
i.e. temperature profiles
1.3.3. Roasting
General Definition: Roasting is the oxidation of metal sulfides to give metal oxides
and sulfur dioxide.
Typical examples are:
2ZnS + 3O2 = 2ZnO + 2SO2, H298oK = -220 Kcal/gm-mole
Strongly Exothermic
o
2FeS2 + 11/2O2 = Fe2O3 + 4SO2, H298 K = -410 Kcal/gm-mole
Reactions
Product ( calcine )
or
12
1.3.3.1.Temperature of Roasting
Troast > 500 - 600C: in order for the reactions to occur with sufficient velocity.
Troast < 1000C: roasting is usually carried out below the melting points of the
sulfides and oxides involved and to avoid ferrite formation.
Dead roast or sweet roast: Roasting to completion with the elimination of most of the
sulfur by overall reaction.
Partial roasting: Removal of some of the sulfur by roasting.
e.g. partial roasting of copper concentrates
CuFeS2 + 4O2 = CuSO4 + FeSO4
2CuS + 7/2O2 = CuO.CuSO4 + SO2
1.3.3.2.Types of Roasting
1. Oxidizing roast
2. Volatilizing roast
3. Chloridizing roast
4. Sulfating roast
5. Magnetizing roast
6. Carburizing roast
7. Sinter or Blast roasting
1.3.3.3.Types of Furnaces for Roasting
Development sequence:
Stationary heaps
- old days
Hand rabbled furnaces - later development
Multiple hearth furnaces long time used for roasting
Flash or Suspension roasting furnaces
Fluidized bed roasting furnaces
Others:
Blast roasting or sinter roasting, roasting in a rotary kiln, etc.
Fluidized bed roasting became the dominant technique for roasting FeS2 (pyrite),
sulfides of Cu, Zn, Co, Ni, etc. in recent years. It is very efficient and close control is
possible.
1.3.4. Agglomeration
When the particle size of an ore or concentrate is too small for use in a later stage of
treatment, i.e. in the blast furnace, it must be reformed into lumps of appropriate size and
strength that is agglomerated. Agglomeration is used particularly if the ore is to be smelted in
a shaft furnace where fine-grained material would plug up the gas passage, i.e. decrease gas
permeability.
Types of agglomeration
i.
Sintering
ii.
Pelletizing
iii.
Briquetting
iv.
Nodulizing
Below sintering and pelletizing of iron ores or concentrates are explained.
13
1.3.4.1. Sintering
Sintering may be defined as a process in which relatively coarse materials, e.g. for
iron ore concentrate 8mm + 0.15mm (100 mesh), are converted into coarse agglomerates by
partial melting and fusion. The sinter product has a porous structure.
Sintering is generally done by the use of a Dwight Lloyd sintering machine.
Sectional-view of a Dwight Lloyd sintering machine is given below.
1.3.4.2. Pelletizing
Pellets are made by rolling critically moist finely divided material around in a drum or
in a rotating inclined disc. Below pelletizing of iron ore concentrate is explained.
i.e. Iron ore concentrate: Particle size 70 % - 325 mesh (44 microns) with
specific surface area, i.e. Blaine Number 1600 2200 cm2/gram
Bentonite (i.e. clay): Binder
Flux : Calcium oxide powder (to control basicity)
14
After the production of green pellets, they are dried and fired at 1200 - 1375C,
i.e. induration, in order to obtain fired pellets of sufficient strength.
For hardening of green pellets, the following pellet firing processes or furnaces are
available:
i.
Shaft furnace
ii.
Grate-Kiln machine
iii.
Travelling grate (similar to Dwight-Lloyd)
iv.
Grate-rotary hearth-shaft furnace
Pelletizing is well suited for very fine grained concentrates which are not easily
sintered on the grate. Pelletizing of chromium concentrates, copper concentrates, etc, are also
being done.
15
Metal sulphides
Matte Smelting
e.g. Cu concentrate
Matte e.g. Cu2S, FeS, etc
20-30% Cu
30-55% Cu
Matte can be defined as molten mixture of sulphides of heavy metals. Liquid slag is
the siliceous or oxidized part of the concentrate.
Matte smelting is done in one of the following furnaces: (Diagrams given below)
- Reverberatory furnace (for fine concentrates)
- Flash furnace (for fine concentrates)
- Blast furnace (for lumpy ore or agglomerated concentrates)
- Electric furnace (for fine concentrates)
Matte smelting is therefore a pyrometallurgical concentrating stage in the overall
extraction of a metal from its sulphides.
Fluxes (Under Reducing Conditions)
Metal oxides
(ore or concentrates)
e.g. Fe2O3, Fe3O4
16
17
Liquid slag contains the gangue minerals and fluxes. It removes the impurities. Liquid
metal, such as pig iron, is an alloy of iron containing C, Si, Mn, etc. Smelting for metal is
done in blast, reverberatory and electric furnaces. Metal oxide smelting is an important
extraction process producing an impure metal which must be subsequently (fire) refined.
Tmatte smelting < Tmetal oxide smelting
1.4.1.2. Converting
Flux
Matte
Converting
Preferential oxidation of the more reactive impurity metal sulphides, e.g. FeS
FeO. Air blowing is controlled to convert the remaining more noble metal sulphide to the
required metal, e.g. Cu2S Cu (blister copper)
Cu2S + 3/2O2 Cu2O + SO2
i. 2MeS + 3O2 2MeO + 2SO2
FeS + Cu2O FeO + Cu2S
FeS + 3/2O2 FeO + SO2
Cu2S + 3/2O2 Cu2O + SO2
ii. MS + 2MO 3M + SO2
Cu2S + 2Cu2O 6Cu + SO2
Cu2S + O2 2Cu + SO2
Cutaway view of a horizontal side-blown Pierce-Smith converter is given below.
18
slag
sulphide matte smelting
preferential oxidation of
and converting
impurity elements
SO2(g)
e.g blister copper
Steelmaking
Slag
e.g. pig iron
19
1.4.1.5. Distillation
Low boiling point (Bpt) metals can be separated and refined from higher boiling point
metals by distillation, i.e. evaporation and subsequent condensation to the pure metal due to
their difference in vapour pressures.
M(l) M(g)
The metals that may be refined by distillation are mainly limited to those with boiling
point less than 1000C. Use of vacuum distillation extends the range of metals that can be
refined.
Separate recovery of vapour
Liquid mixture
Distillation
Residue
Partial Vaporization
e.g. Extractive metallurgy of zinc and mercury (Hgbpt : 357C)
Removal of As (arsenic) from (iron ores) liquid iron (fractional distillation)
Vacuum dezincing (Znbpt : 907C) of desilverized lead bullion (Pbbpt :1740C)
1.4.1.6. Halide Metallurgy
By using halogens (Cl, Br, F, I) metal halides (chlorides, iodides, fluorides, bromides)
are formed.
Zircon
ZrSiO4
Chloridizing
roasting
ZrCl2
Reduced with Mg
Zirconium
metal
or some volatile metal halides are produced, e.g. SnCl4, TiCl4, AlCl3
some metal halides have low decomposition temp.
ZrI4 Zr + 2I2 , @ 1400C
Therefore, it is possible to separate certain metal halides and to purify by distillation.
1.4.2. Hydrometallurgy (Water Metallurgy)
1st definiton: Hydrometallurgy is concerned with the leaching of ores, concentrates
and calcines with aqueous solutions to dissolve and recover the valuable metals.
2nd definiton: The separation of a soluble substance from an insoluble by means of a
solvent. The solvent is either water or an aqueous solution.
Essential steps
Auxiliary step
1.4.2.1. Advantages
-
BUT
1.4.2.2. Solvents
Requirements
i.
It must dissolve the ore minerals rapidly enough to make commercial
extraction possible, and it should not attack the gangue minerals.
ii.
It must be cheap and readily available in large quantities.
iii.
If possible, it should be regenerated.
Some solvents
i.
Water
ii.
Acids
iii.
Bases
iv.
Salts
v.
Bacterial
leaching
22
scrap iron
Cadmium sponge
Electrochemical Series (25C, 1 N solution) volts
+ 3.095 Cr
+0.744 Pb
Li / Li+
2+
K
+2.925 Fe/Fe +0.440 H2/H+
Na
+2.714 Cd
+0.403 Cu / Cu2+
Mg
+2.363 Co
+0.277 Hg
Al
+1.662 Ni
+0.250 Ag
Zn
+0.763 Sn
+0.136 Au
23
+0.126
0.000
- 0.337
-0.788
-0.799
- 1.680
valency=n
(Ni++ + H2 Ni + 2H+)
precipitate
NaAlO2 + 2H2O Al(OH)3 + NaOH (Hydrolysis reaction)
(without reduction)
Solvent Extraction (SX): Liquid liquid extraction (liquid ion exchange) LIX
(For solution concentration or purification purposes)
Aqueous solution
+
organic
mixing for SX
(insoluble in leaching solution, capable of separating
(pregnant solution)
from leach solution, must be highly selective)
Extraction in various
organic
Di(2-ethylhexyl)phosphoricacid
(DEHPA)+kerosene
types of mixing units
(stirred tanks, columns, etc.)
contact with leach solution containing uranium
Uranium Crushing
ore
& grinding
Leaching
with H2SO4
1g/l U3 O8
DEHPA
Leach residue
mixer settler raffinate
(SX)
6 g/l U3O8
loaded organic
HCl stripping regenerated organic
100g/l U3O8 (after stripping)
NH3 ppt
(NH4)2U2O7 (ADU)
Ion Exchange (IX): Generally used for low grade uranium ore processing, water
softening, processing of rare-earth metals, etc.
e.g. Water Softening
Water Zeolite (sodium aluminate-silicate) removes Ca/Mg from water softened water
IX resin
by exchange with Na
e.g. IX of Uranium
pregnant solution + synthetic resin IX
(with uranium)
(organic polymers, e.g. Amberlite IRA 425, Dowex 11, etc.)
24
resin
Uranium
ore
R4(UO)2(SO4)3 + 4X
negative ion
Elution with
NaCl, HCl eluent
H2SO4
resin
(eluate) recovery
leach
effluent
residue
to waste
regenerated resin
1.4.3. Electrometallurgy
Electrometallurgy deals with metallurgical processes that require electric current for
chemical reduction.
Electrolytic refining (e.g. Cu, Fe, Co, Pb, Zn, etc)
i.
Electrolysis
Fused salt electrolysis (e.g. Al2O3, MgCl2 etc)
( production of Na, Zr, Ti, K, Ca, etc )
ii.
25
26
SUMMARY
General Classification of Ores for Leaching
Barren solution
(Solvent)
In-Place Leaching
Pregnant
leach liquor
Mineral Deposit
Transported for Leaching
Dissolution
Separation
Direct Leaching
Ore
Mineral Dressing
Pretreatment (optional)
Dissolution
Dump, Heap, Vat
Leaching
Concentrate
Pretreatment
Separation
e.g. Cu dump leaching
Leaching of waste products
not economic to subject them
to additional treatment.
e.g. fine grinding,
concentration, etc.
e.g. Production of
Uranium, Vanadium
Gold, Silver
Aluminum
Nickel
Beryllium
Titanium
Cobalt
27
(optional)
Dissolution
Separation
e.g. Production of
Zn, Cu, Ni, Co, W
Pt, Ti, Mn, Mo
Ore or
concentrate
Dilute process
stream
Concentrated
liquor
Solvent Extraction
Ion Exchange
Precipitation
by reduction
Hydrogen
Ni, Co, Cu
M2+ + H2 M + 2H+
Precipitation
without reduction
Uranium, copper
Electrowinning
Cu, Zn
28
As salts, sulfides
-Uranium (Na2U2O7)
(as yellow cake)
-Fe, Co, Cu, Ni
as hydroxides
-Aluminum as Al(OH)3
-Ppt of Mg, Be, etc.
Energy
For
Smelting
Reduction
Handling
Comminution
Separation etc
1.5.1. Fuels
1.5.1.1. Definitions
A fuel is any substance (it may even be a metal) that may be burned rapidly enough so
that the heat resulting from the oxidation is capable of being applied to industrial operations.
Combustion is the term applied to the burning of fuel.
Incomplete combustion is a term applied to combustion in which not all the fuel is
burned (leaving unburned carbon in ashes for example).
Imperfect combustion means that not all the fuel is oxidized to its highest degree (if
CO is formed, for example instead of CO2).
Ignition temperature of fuel is the temperature at which combustion starts. This is not
definite and it depends upon the physical condition of the fuel and atmospheric pressure.
Ashes and cinders are the residue left after the fuel has burned.
1.5.1.2. Heat Producing Elements:
These are given by the order of importance as:
C, H, S, Si, Mn, Al, and P.
C is used in the elemental form (charcoal, coke), combined form (hydrocarbons) and
partly free, partly combined form (lignite and bituminous coals).
H occurs in its free state in some gaseous fuels, or combined as in hydrocarbons.
S is important in roasting and in matte converting as the fuel but is undesirable as an
impurity in the finished metals (for example in steel).
Fe2O3+SO2
e.g. Used for
Sulphide Concentrate Roasting Heat Evolved steam production
e.g. FeS2
(exothermic)
Sometimes enough heat evolved to sustain the process.
e.g. Autogenous roasting of FeS2, sintering of PbS, etc.
i.e. No carbonaceous fuel added.
29
30
1.5.2. Refractories
1.5.2.1. Definitions
Refractory materials or refractories are those materials that can withstand high
temperatures, corrosion from liquids and abrasion of hot gases laden with dust.
Acid refractory or acid oxide is one which will absorb oxygen ions when dissolved in
a basic melt:
SiO2+2O2 = SiO44Basic refractory or basic oxide is one which will provide oxygen ions when dissolved
in a melt:
MgO= Mg2+ +O2Neutral refractory is a material that is attacked by neither acidic nor basic oxides and
is used to replace basic refractories where the corrosive action is strong.
1.5.2.2. Refractory Materials
The commercial refractories are based on either of the following substances:
1. Silica (SiO2)
2. Alumina (Al2O3)
3. Aluminosilicate (xAl2O3.ySiO2)
4. Lime (CaO)
5. Magnesia (MgO)
6. Forsterite(2MgO.SiO2)
7. Dolomite ( MgO.CaO)
8. Hematite (Fe2O3) or Magnetite (Fe3O4)
9. Chromite (FeO.Cr2O3)
10. Carbon (Graphite)
11. Metals (Water-cooled)
12. Carbides (Silicon carbide and others)
1.5.2.3. Melting Point of Refractories
Silica
1724C
Kaolin
1740 C (High Al2O3 clay)
Bauxite Brick
1600-1820 C (High in Al2O3)
Alumina
2050 C (corundum)
Magnesia Brick 2165 C
Chromite
2050-2200 C
Silicon Carbide (beyond 2700 C)
Carbon
solid at 3600 C
The softening points of refractories, not their melting points should be considered
when selecting a refractory for the lining of a furnace.
Temperatures Attained in some Metallurgical Process
Copper Smelting
1000- 1100 C
Zinc Retorts
1400- 1600 C
Bessemer Converter
1600 C
Oxygen Converter
1850 C
Tuyeres in Fe Blast Furnaces
1900 C
Electric Arc Temperature
3600 C
Electric Arc Furnace for Steelmaking
1800 C max
31
32
Resistance to Chemical Attack: Most of the oxide or silicate refractories are already
fully oxidized so that they will not be affected by oxygen. However, graphite and silicon
carbide will oxidize at high temperature and actually will burn.
Chemical attack usually results from the contact of acid and basic refractories, through
slag or dust. With acid slag (i.e. slag high in silica) acidic refractories and with basic slag (i.e.
high in CaO, MgO) basic refractories should be in contact. The product of the chemical
reaction has a very low melting point (forms a eutectic). For the same reason acid and basic
refractories should not be laid side by side in the heated portions of the furnace. Bricks may
have to withstand abrasive damage or erosion by fast moving, dust-laden gases.
Softening Point: It is the temperature at which, the refractory is plastically deformed
under load. The selection of the refractory for a given service temperature should take the
softening point into consideration not the melting point of the refractory.
Ability to Stand High Temperatures: Refractories should stand high temperatures.
33
Slag
CaO
SiO2
Al2O3
MgO
Pig Iron
Main product of blast furnace
C
3.5 4.25 %
Mn
0.5 2.5 %
Si
1.0 3.0 %
S, P, etc.
0.025%
Fe
Rest
Raw Materials
1. Coke: Fuel+Reducing agent
( -7.5 cm + 1.5 cm)
2. Limestone: For slag formation
+ Removal of impurities
(-7.5 cm +2.5 cm)
3. Source of Iron
Iron ore Fe>51%
-75mm +8mm
35-45%
30-35%
10-15%
2-10%
and/or
Sinter -50mm +8 mm
and/or
Pellets 10-12 mm
34
1.7. STEELMAKING
Steelmaking is an intermittent process.
Steel is an alloy of iron and C (max 2%C)
Most steels contain< 0.6% C
Steel Making Processes
1. Bessemer Process(Acidic)- Thomas Process (Basic)
2. Open-hearth Steelmaking (Siemens-Martin Furnaces)
3. Oxygen Steelmaking- L.D., LD-AC, Kaldo, Rotor, etc. (Ereli, skenderun,
Karabk)
4. Electric Steelmaking (ukurova, Asil elik, Kroman, emta, etc.)
Mpt
1250-1450oC
BF
Pig Iron
Acid Steelmaking
(S,P-cant be removed)
Basic Steelmaking
(S,P can be removed)
35
Comminution
Flotation Tailing
Cu Concentrate (20-30%Cu)
or
Drying
Electric
Furnace
or
Roasting
Ergani
or
Green Conc.
Murgul
Reverberatory
Furnace
or
Drying
KBI
Flash
Furnace
or
Sintering
or
Pelletizing
Cu Blast
Furnace
(99.99 %Cu)
36
or
Continuous
Process
Lean Ore
(Cu<1.0%)
Rich Ore
(1-2 %Cu)
Heap Leaching
with H2SO4
Vat Leaching
with H2SO4
Pregnant Leach
Solution (5 kg Cu/m3)
Cementation
by scrap
SX
Cement Cu
Electrolyte
(40 kg Cu/m3)
Electrolyte
(35 kg Cu/m3)
Electrowinning
37
Oxide Concentrate
or
Roasted Sulphide
(20-30 %Cu)
Agitation
Leaching
Electrolyte
(40 kg Cu/m3)
Fluxes
-6 mm CaCO3
CaCO3 CaO+CO2- Heat
At 1100 C
Dust Laden Gases
containing SO2
Sinter
Coke (fuel)
Air
Scrap Lead Blast Furnace
(For slag formation)
1400oC
Slag (SiO2, FeO,
ZnO, CaO etc.)
SO2
Dust
H2SO4
BF gas
Waste
Commercial Pb
Reduction in Blast Furnace:
PbO + CPb + CO
PbO + CO Pb + CO2
38
Hydrometallurgical Route
ZnS Concentrate
Roasting
(50%Zn)
(ZnS+3/2O2 ZnO+SO2+heat), T:900C
Roasting
Pressure Leaching
under O2
ZnO+H2SO4ZnSO4+H2O
Solid
(Leach Residue)
Liquid
Solution Purification
Cd,Cu,Co,Ni,etc
separated
Electrolysis
2ZnSO4+2H2O+2e-2Zn0+ 2H2SO4+O2 Anodes: Pb or Pb-Ag
Cathodes: Al
Slab Zn
Reduction Reaction:
ZnO + C Zn +CO
ZnO + CO Zn +CO2
Electrolytic Zinc
99.99% Zn
39
Al2O3+2NaOH
2NaAlO2+H2O
T up to 300oC
P up to 40 atm.
Seeds
Al(OH)3
Separation of Al(OH)3
2 Al(OH)3 Al2O3+3H2O
3NaF.AlF3
(cryolite)
Al2O3 (99.6%)
Electrometallurgy
Fused Salt Electrolysis
Aluminum Metal
>99.5% Al
At the Cathode:
Al2O3 2Al + 3/2O2
At the Anode:
C + O2 CO2
C + O2 CO
40