PYROMETALLURGY -2

1. Termodinamika dan kinetika

2. Preliminary Treatment
3. Smelting Process and Furnace

THERMODYNAMICS AND KINETICS

IN
EXTRACTIVE METALLURGY

References
1. M. A. Rhamdhani, Appplication of
Thermodynamics to Industrial Processes,
Workshop materials, Swinburne Univ. of
Technology, 2012
2. C. K. Gupta, Chemical Metallurgy: Principles
and Practices, Willey-VCH, 2003
3. M. Bahrens, Solid State Kinetics, Lecture
materials, Fritz Haber Institute, 2012

Content
Thermodynamics Fundamentals
Definitions and Basics Concepts
Energy, Energy Transfer and general energy
analysis
0th law, 1st law, 2nd law and 3 rd law of
thermodynamics
Ellingham Diagram

Content
Solid state Kinetics Fundamentals
Basics kinetic
Solid defects
Solid reactivity

Decomposisition reactions, sintering

Solid gas reaction
Solid solid reaction
Solid liquid reaction

Thermodynamics
Thermodynamics Science of energy
Therme: heat and dynamis: power

All activities and processes in nature involve

some interaction between energy and matters

(source: Ref [1])

Thermodynamics
Classical thermodynamics:
A macroscopics approach to the study of
thermodynamics that does not require a knowledge
of the behavior of individual particles
It provides a direct and easy way to the solution of
engineering problems

Statistical thermodynamics:
A microscopic approach, based on the average
behavior of large groups of individual particles
More difficult but potentially better for predicting
behavior of a system.

(source: Ref [1])

Definitions
The theory assume that Universe consist of
system and surroundings,i.e.
Universe = System + Surroundings
System: a quantityof matter or a region in
space chosen study
Surroundings: the region outside the system

Surroundings

Boundary: surface that separates the

system from its surroundings (can be real or
imaginary, fixed or movable)

System
Boundary

(source: Ref [1])

Closed, open, and Isolated Systems

Closed (control mass):
No mass enter or leave the system.
Energy may cross the boundaries.

Open (control volume):

Mass and energy can enter/leave the
system.

Isolated: No mass and energy

can enter/leave the system.

(source: Ref [1])

Other Definitions
Property any characteristics of a system.
Example: pressure P*, temperature T*, volume V and mass m

Thermal: thermal conductivity, thermal expansion

Electrical: electrical conductivity
Physicochemical: viscosity, surface energy, density
Mechanical: modulus of elasticity, strenth

Note: *In thermodynamic calcualtion, always use absolute

temperature and pressure

State definition of a system (has certain properties)

Process when property(ies) change thus change of state
(source: Ref [1])

Energy
Various forms: Thermal, Mechanical, Kinetic, Potential,
Electrical, Magnetic, Chemical, Nuclear
In SI system in Joule (J) or kJ
sometimes express per unit mass (J/g) or unit time
(J/s=watt)
Can be classified:
Macroscopic Those a system posseses a whole with
respect to some outside reference frame, e.g. PE, KE
Microscopic related to the mo;ecular structures and
activities internal energy (U)
(source: Ref [1])

Internal Energy, U
Sensible energy: the internal
energy associated with the
kinetic energies of the
molecules.
Latent energy: the internal
energy associated with the
phase of a system.
Chemical energy: : the internal
energy associated bonds in a
molecule.
Nuclear energy: the
tremendous amount of energy
associated with the strong
bonds within the nucleus of
atom itself.
(source: Ref [1])

Thermal = sensible + latent

Internal = sensible + latent + chemical + nuclear

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

(source: Ref [1])

Variation of free energy and

temperature
Standard free energy change is expressed by equation:

G0 = - R T ln K

By the corresponding entropy (a measure of degree and enthalphy

change by the relation:

G0 = H0 T S0 ---- y = m x + c
Note:
Entropy: quantitative measure of the amount of thermal energy not available
to do work/ a measure of disorder in closed system
Enthalphy: heat content

Ellingham diagram
Line 1:
-Endothermic reaction with
entropy decreasing (G is always
positive)
-Line 3:
-Exothermic reaction with entropy
decreasing (the slope is positive)

-Line 2:
-Endothermic reaction with
entropy increasing.
-Line 4:
-Exothermic reaction with entropy
increasing.

Ellingham diagram

Ellingham diagram
Line 1:

a typical case of phase

transformation of reactant.
Line 3:
a typical case of phase
transformation of product.

Ellingham diagram

KINETIKA DALAM METALURGI

EKSTRAKSI

Referensi:
Solid State Kinetics
Malte Behrens

Fritz Haber Institute of the Max Planck Society

Department of Inorganic Chemistry
behrens@fhi-berlin.mpg.de

HEAT GENERATION
SUMBER DAN PEMBANGKIT PANAS

COMBUSTION OF CARBONACEOUS
FUELS
Heat is generated during the combustion of
carbonaceous fuels by air or oxygen
The quantity of heat generated on complete
combustion of a unit weight of fuel calorific
value
Heat is transferred to the charge by
conduction, convection, radiation

Calorific Value of fuel

Generation of Heat
when carbonaceous fuel is burned by the
stoichiometric amount of air, there is always a
fraction that escapes combustion due to:

o the design of the reactor

o kinetics of the reaction itself
This represent heat loss

Generation of Heat
Carbonaceous fuels can be solid, liquid, or
gaseous.
In metallurgy, gaseous fuels are more
preferable than the types. Why??
Easily stored
can be obtained free from sulfur
leave no solid residue on combustion (ash)

Generation of Heat: coal

Coal, basic raw material which can be
converted to a liquid fuel (coal liquefaction)
by reaction with hydrogen under pressure, or
to a gaseous fuel (coal gasification) by
reaction with air and water vapor.
Types of coal: charcoal prepared by the
carbonization of wood, and mineral coal that
occurs in nature.

Generation of Heat: coal

Sulfur in coal is a problem of special
importance because it is a source of pollution
when coal is burned, and source of
contaminating metals during their production.

Generation of heat: gas

Natural gas is a mixture of hydrocarbons that
occurs in nature in underground reservoirs.
CH4 = 50 90% other CnHm
Small amount of N2 and CO2
Variable amount of H2S. It is removed from
gaseous fuels by: passing the gases over a bed
of heated ferric oxide which reacts forming a
mixture of iron sulfides:
Fe2O3 + 3 H2S FeS + FeS2 + 3 H2O

http://www.energy
.alberta.ca/Natura
lGas/723.asp

Generation of heat: electric heating

Achieved by the following method:
Resistance heating based on the resitivity of
the medium when an electric current is passed
through.
Graphite electrode carrying the current may be
used in the following way
Above the solid feed
Immersed in slag layer
Contacted to a solid charge

TUNGKU PELEBURAN METALURGI

Metallurgical Furnace

Hearth Furnace
Vertical Furnace
Horizontal Furnace
Rotary Kilns
Retort Furnace
Moving Grate Furnace
Multiple Hearth Furnace
Fluidized bed Furnace
Tunnel Furnace
Induction Furnace
Plasma Furnace

1. Rotary kiln

1. Rotary kiln
Applications:
Roasting and calcining
Iron ore reduction
Ilmenite reduction

2. Multiple hearth furnace

3. Shaft furnace

4. Smelting, melting and refining in

bath and flash smelting reactor

www.tms.org

5. Electrothermal reactor

Resistance Furnace
Arc Furnace
Induction furnace
Electron beam furnace
Plasma furnace
Laser beam furnace

6. Electron beam furnace

7. Fused salt electrolytic

cell

REFRAKTORI

Refractory

Refractory

Refractory
Properties:

Refractory

Refractory

PROCESS:
PRELIMINARY, SMELTING, REFINING

Preliminary Treatment

Preliminary Treatment

Thermal Pretreatment
Alkali Fusion
Sulfation of Oxide
Oxidation of Sulfide
Matte Formation
Chlorination
Fluoration

Alkali Fusion
Alkali fusion ini merupakan metode yang
melibatkan pemanasan bijih atau konsentrat
dengan suatu alkali atau alkali tanah untuk
mengkondisikan mineral yang berharga siap
untuk dilakukan proses berikutnya. Metode ini
biasa digunakan untuk oksida dan batuan
silikat dan pada sedikit sulfide

Alkali Fusion
Reagent
CaO
CaO-Na2CO3*
NaCl
Na2CO3

Melting Point 0C
2580
800
801
851

Na2SO4
NaOH

884
318.4

Na2S**

1180

Aplikasi
Clays, Spodumene, Zircon
Clays, Beryl
Vanadium dari Carnotite
Bauxite, Clays, beryl, Chromite,
Wolfarmite
Radium dari pitchblende
Beryl, Nb-Ta Ores, pasir zircon
Sulfida

Alkali Fusion
Alkali fusion pada bauxite untuk menghasilkan aluminium,
digunakan sebelum penemuan Bayer dengan metode
pressure leaching. Pada proses ini, bahan baku halus
diaduk dengan Na2CO3 dan CaO secara merata dan lalu
dipanaskan di rotary kiln pada 1000 0C. dimana aluminium
akan menjadi sodium aluminat.
2 Al(OH)3 + Na2CO3 2 NaAlO2 + CO2 + 3 H2O
Ketika CaO bereaksi dengan SiO2 dalam batuan maka akan
membentuk dikalsium silicate yang tidak larut air.
2 CaO + SiO2 Ca2SiO4

Alkali Fusion
Mineral Fe dan Ti juga akan menyisakan senyawa
yang tidak larut juga. Proses ini juga bisa
digunakan untuk mengekstrak aluminium dari
clays, seperti kaolinite, Al2(Si2O5)(OH)4, dan
nepheline syenite, (Na,K)(Al,Si)2O4. Reaksi dengan
kaolinite bisa dilihat pada persamaan dibawah ini.
Al2(Si2O5)(OH)4 + Na2CO3 + 4 CaO 2 Na2AlO2 +
2 CaSiO4 + CO2 + 2 H2O

Outline

Reduction of Nonferrous Oxides

Reduction of Halides
Reduction of Sulfides
Conversion of Sulfides

Reduction of Nonferrous Oxides

Introduction
Nonferrous Oxides reduced by carbon on an
industrial scales are those of lead, zinc, and tin
and to minor extent are those of copper,
antimony, arsenic, nickel, and magnesium.

Nonferrous oxides reduced by hydrogen are

those of molybdenum and tungsten.
while those reduced by metals are the oxides of
magnesium,
boron,
and
vanadium
(metallothermic reactions).

Oxides Reduced by Carbon

Lead Oxide
Lead sulfide the major lead ore is usually
oxidized to oxide which is then reduced by
coal to metallic lead in a blast furnace.
Rx:

PbO + CO Pb + CO2
CO2 + C 2CO

Oxides Reduced by Carbon Lead Oxide

To prevent unwanted reaction (ex: Cu),
enough sulfur is maintained in the charge so
that copper can be separated as a matte.

Oxides Reduced by Carbon Lead Oxide

Oxides Reduced by Carbon Lead Oxide

Oxides Reduced by Carbon Zinc Oxide

Zinc Oxide
Zinc Oxide is obtained by the oxidation of ZnS
concentrate. Low grade zinc oxide and carbonate
ores occur in nature <5% of zinc production.
2 ZnO + C 2 Zn + CO2
ZnO + C Zn + CO

Oxides Reduced by Carbon Zinc Oxide

An important feature of the reduction of ZnO
is the fact that the reduction temperature is
above the boiling point of zinc which is 906
C. Zinc is thus obtained in the vapor phase
from which it must be condensed.
Zinc vapor is very susceptible to oxidation by
water vapor or CO2 arising from the reduction
reaction.

Oxides Reduced by Carbon Zinc Oxide

Reduction is conducted by a variety of
methods: product 97% Zn and is always
followed by refining.

Oxides Reduced by Hydrogen

The most important nonferrous oxides
reduced by hydrogen on an industrial scales
are MoO3 and WO3. Both are volatile at high
temperature.

Oxides Reduced by Metals

The Three Steps of the Pidgeon Process (magnesium oxide)
1.

Calcination of Dolomite,
CaMg(CO3)2 = CaO + MgO + 2CO2

2.

Ferrosilicon Alloy Production ,

Fe2O3 + 4SiO2 + 11C = 2(Fe)Si2 + 11CO

3.

Silicothermic Reduction of MgO by Ferrosilicon,

2MgO + 2CaO + (Fe)Si = 2Mg(g) + Ca2SiO4(s) + Fe

Reduction of Halides

Introduction
Metals produced by the reduction of their
halides are usually the reactive metals that
cannot easily be prepared by the reduction of
their oxide.
Halide of these metals may be reduced by
hydrogen or by metals.

Reduction of Sulfides

Reaksi konversi
Transformasi sulfida logam menjadi logam oleh udara atau
oksigen.
Mekanisme:
2 MS + 3/2 O2 MO + SO2
(exotermik)
2 MO + MS
3 M + SO2
(endothermik)
--------------------------------------------- MS + O2 M + SO2
(exothermik)

Tembaga:
2 Cu2S + 3 O2 2 Cu2O + 2 SO2 H = -184 kcal
2 Cu2O + Cu2S 6 Cu + SO2
H = + 28 kcal
Cu2S + O2 2 Cu + SO2
H = - 52 kcal

Syarat terjadi reaksi konversi

Sulfida dapat dipanaskan hingga temp
tertentu pada laju pemanasan yang memadai
tanpa volatisasi.
Oksida yang terbentuk harus bisa melarut
dalam leburan sulfida sehingga interaksi
sulfida-oksida terjadi dengan cepat.
Logam yang terbentuk tidak boleh larut dalam
leburan sulfida-oksida sehingga membentuk
lapisan terpisah dan mendorong reaksi ke
kanan.

Diagram fasa Cu Cu2S

Smelting
Ada 2 jenis peleburan:
Reduction smelting menghasilkan logam cair tak murni dan
terak cair hasil reaksi logam oksida dan reduktor;
Matte smelting campuran cairan logam sulfida dan terak.
Jenis dapur:
Reverberatory/oxygen reverberatory furnace
Electric furnace
Flash smelting
Continous smelting
Blast furnace/low shaft blast furnace

Reverberatory smelting

- Reverberatory smelting are used for the matte smelting of fine flotation concentrate,
Where a relatively quiet operation is desired that will not blow too much of the fine
feed material out of furnace

Outokompu Flash smelting

Blast furnace

Reverberatory type of flash smelting furnace

(Inco)

Continous matte smelting and converting

furnace (mitsubishi process)

Smelting Electric furnace (nickel)

Stationary furnace

Cylindrical rotary furnace

Comparison of smelting process

Converting

Converting

Stationary smelting-converting

Top blown Rotary converter

(Hoboken siphon converter)

Cylindrical rotating smeltingconverting

REFINING

Slow cooling refining

Dross refining

Electro refining

Electrolytic cell