Material Balances

Flow Sheet
• The process or combination of processes which is
used in a given plant is illustrated conveniently by
means of a flow sheet.
• The flow sheets consist of combinations of steps
or operations and that some of the same steps or
operations are found in the production of
different metals and in different locations.
• Flow sheets for the production of cupper, steel
and zinc are shown in figure 1-1 until 1-3.
Unit Processes and Unit Operations
• The steps characterized by a certain chemical
reaction are called by unit processes and the
steps which are characterized by certain physical
features are called by unit operations
• Classification step is more difficult in extractive
metallurgy than in chemical engineering
• There are 3 major types of classification could be
considered in extractive metallurgy process.
 3 Major Types of Classification
According to Phases Involved
• Gas-Solid (Roasting, gas
reduction)
• Gas-Liquid (Bassemer blowing,
distillation)
• Liquid-Liquid (Slag-Metal
Reactions
• Solid-Liquid (Liquation, leaching,
precipitation)
According to Equipment
• Fixed Bed (sintering, percolation
leaching)
• Fluidized bed (fluidized roasting
and reduction)
• Shaft furnace (iron blast furnace,
lime kiln)
• Rotary Kiln (drying, calcination)
• Retort (coke oven, carbothermic
zinc production)
• Reverberatory furnace (matte
smelting, open hearth
steelmaking)
• Electric Furnace (Electric Matte
Smelting and Steel making)
According to Chemical Reactions
• Oxidation (roasting, sintering,
bassemer blowing)
• Reduction (iron-making,
carbothermic zinc production)
• Slag-Metal reactions (steel
making, matte smelting)
• Chlorination (Production of
titanium tetrachloride)
• Electrolytic Reduction
(electrolytic zinc and aluminum
production)
• Electrolytic Refining (refining of
copper and nickel
 Material Balances
• Materials balances is a form of book-keeping
for a process which is already operating.
• The basic equation in material balances is the
law of conservation of matter.
mi = raw material which enters
mj = the mass of each product which leaves the process
Input = Output + Accumulation
%x = weight percentage of element x in that raw material or product

If the = 0, we say that steady state conditions exist

Material Balance Under Steady State Conditions

A+B+C = L+M+N
Raw Materials = Products
Component
=
A B C L M N

x mA (%x) + mB (%x) + mC (%x) = mL (%x)+mM (%x)+mN(%x)

y mA (%y) + mB (%y) + mC (%y) = mL (%y)+mM (%y)+mN(%y)

z mA (%z) + mB (%z) + mC (%z) = mL (%z)+mM (%z)+mN(%z)

 Production of Basic Flowsheet
Identifying the
Formulating
basis of the Assumptions
the problem
calculation

Solution Preliminary
Strategy Calculations
Every metal and every locality required its own extraction process

Source : Principle of Extractive Metallurgy, Rosenqvist

Langkah penyelesaian soal
 Example 1-1
A copper ore contains 1.5%Cu. After ore
dressing, 4.5 kg of concentrate with 30% Cu is
obtained from 100 kg of ore. Calculate :
a) Ratio of the concentration
b) The recovery
c) The weight and Cu percentage of discarded
gangue (tailing)
 Solution 1-1
a) The ratio of concentration is given by 4.5/100 =
0.045
b) The ore contains a total of 0.015 x 100 = 1.5 kg
Cu. The concentrate contains 0.30 x 4.5 = 1.35
kg Cu. This given the recovery = 1.35/1.5 = 0.90
= 90%
c) The weight of the tailing is 100 – 4.5 = 95.5 kg
and in copper content 0.15 kg. This given its Cu-
Percentage equal to 0.157
Example 1-2
Solution 1-2
Solution 1-2
Energy Balances
 Introduction
• Energy and heat balances are key elements in the
design and selection of chemical processes and
processing routes
• The net heat balance on a process is therefore of
vital importance to process control
• The analytical techniques are based on the first
law of thermodynamics which, in its simplest
form, states that energy is conserved.
 Enthalphy Balances
• Consider the simple case of a closed system,
where there is no mass transfer across the
system boundary
• This change in energy can be directly equated
to the change in internal energy of the system
dU
dE = dU = dq + dw
The statement of the Firs Law of Thermodynamics for a closed system
 Enthalpy Balances
dE = dU = dq + dw
The statement of the Firs Law of Thermodynamics for a closed system
dU = dq – pdV .......... (1)
Enthalpy = H
H = U + pV
dH = dU + pdV + Vdp .......... (2)
For conditions of constant pressure, dp = 0 and from the addition of
equation (1) and (2)
dH = dq p
 Enthalpy Balances
dH = dq
p

The transfer of heat to or from a system at

constant pressure can be directly related to
change in enthalpy
Enthalpy is a thermodynamic property and can
be expressed in terms of temperature and
pressure, its total differential will become
 Enthalpy Balances
• As indicated for most metallurgical systems, where
pressure is nearly constant,
can be neglected. Thus

• By definition, is the heat capacity at constant pressure,

given the special symbol C p

• Changes in enthalpy can then be calculated by integration

of equation
 Heat Capacity
• Normally a function of temperature and presented in
polynomial from such as
Cp = a + bT + CT-2
• As with internal energy, it is impossible to measure the
absolute value of the enthalpy of a substance.
• The reference conditions used in the steam tables are
liquid water at 00C and its vapour pressure.
• In metallurgical and inorganic processes, however, the
most common practice is to choose pure element at
298K and 1 atm pressure as the standard state.
 Example
Calculate the enthalpy change for heating α –
titanium from 298K to 1000K, and also
calculate the enthalpy of α-titanium at 1000K.
The heat capacity of α-Ti at 1 atm is given by the
equation
Cp = 22.1 + 10.4 x 10-3T J/molK
 Solution
The enthalpy change can be found using equation
Enthalpy Changes for Phase Transitions
• The enthalpy change associated with this phase
transformation is called the heat of
transformation, and is directly related to the
change in entropy or disorder of the substance on
transformation.
• Particular examples of heatss of transformation
are : the heat of fusion (melting), the heat of
vaporation, the heat of solution, and the heat if
ionisation.
Enthalpy Changes for Phase Transitions
• The energy added to or subtracted from a
system changes the enthalpy of the system.
• When a phase change from state A to state B
occurs at Tt while heating an objecy from T1,
past T1 to T2, the change in enthalpy will be
 Example
Calculate the elthalpy change of chromium on
heating from 1500K to 2500K. Chromium
melts at 2130K with heat of fusion of 20.9
kJ/mol. Heat capacities of solid and liquid
chromium are given below.
Cp (s) = 24.4 + 9.88 x 10-3 T – 3.68 x 105 T-2 J/molK
Cp (l) = 39.3 J/molK
 Solution
• The enthalpy change can be found using
equation

Where is the heat of fusion

Then

= 163,713 J/mol Cr
 Heat of Formation and Heat of Reaction
• The heat of reaction is the amount of heat
liberated or absorbed during a chemical reaction.
Consider ther following reaction as an example :
2CuFeS2 + 6.5O2 = 2 CuO + Fe2O3 + 4SO2
The quantity of heat liberated when 2 moles of
chalcopyrite (CuFeS2), combine with 6.5 moles of
oxygen to yield 2 moles of cupric oxide, 1 mole of
ferric oxide and 4 moles of sulphur dioxide at
constant temperature and pressure is known as
the heat of reaction
 Example
Find the heat of reaction at 1200K for the
following reaction:
Fe2O3(s) + 3CO(g) = 2Fe(s) + 3CO2(g)
The enthalpy data for the individual species at
1200K are given below :
H Fe2O3 = -692,020 J/mol
H CO = -82,220 J/mol
H CO2 = -349,730 J/mol
H Fe = + 36,950 J/mol
 Solution
Since the heat of reaction is equal to the
enthalpy of the final state minus the enthalpy
of the initial state,