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Fundamentals of
Material Balances
Material Balance-Part 1
Process Classifications
3 type of chemical processes:
- Concept of boundary of the process
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n Prof. Shoukat Choudhury
n 2
Process Classifications
2. Continuous process
– Input and output is continuously fed and
remove from the process
– Operate in steady state
– Used for large scale production
3. Semibatch process
– Neither batch nor continuous
– During the process a part of reactant can be
fed or a part of product can be removed.
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n Prof. Shoukat Choudhury
n 3
2 type of process operations:
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n Prof. Shoukat Choudhury
n 4
Try This…
Define type and operation of processes
given:
• A balloon is being filled with air at steady
rate of 2 g/min
Semibatch and unsteady state
• A bottle of milk is taken from the
refrigerator and left in the kitchen
Batch and unsteady state
• Water is boiled in an open flask
Semibatch and unsteady state
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n Prof. Shoukat Choudhury
n 5
General Balance Equation:
INPUT + GENERATION – OUTPUT – CONSUMPTION = ACCUMULATION
• Steady state;
accumulation = 0
INPUT + GENERATION = OUTPUT + CONSUMPTION
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n Prof. Shoukat Choudhury
n 6
Example
4.2-‐2
One
thousands
kilogram
per
hour
of
a
mixture
of
Benzene
(B)
and
Toluene
(T)
containing
50%
Benzene
by
mass
is
separated
by
a
disEllaEon
into
two
fracEons.
The
mass
flow
rate
of
Benzene
in
the
top
stream
is
450
kg/h
and
that
of
Toluene
in
the
boIom
stream
is
475
kg/h.
The
operaEon
is
at
steady
state.
Calculate
the
unknown
components
flow
rates
in
the
output
streams.
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Flowchart
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n Prof. Shoukat Choudhury
n 9
Flowcharts
• When you are given process information and
asked to determine something about the
process, it is essential to organize the
information in a way that is convenient for
subsequent calculations.
• The best way to do this is to draw a flowchart
– using boxes or other symbols to represent process
units (reactors, mixers, separation units, etc.)
– lines with arrows to represent inputs and outputs.
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n Prof. Shoukat Choudhury
n 10
Flowcharts……
• The flowchart of a process can help get material balance
calculations started and keep them moving.
• Flowchart must be fully labeled when it is first drawn,
with values of known process variables and symbols for
unknown variables being written for each input and
output stream.
• Flowchart will functions as a scoreboard for the problem
solution: as each unknown variable is determined its
value is filled in, so that the flowchart provides a
continuous record of where the solution stands and what
must still be done.
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n Prof. Shoukat Choudhury
n 11
Step 1.2: Labeling a flowchart
100 kmol/min
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n Prof. Shoukat Choudhury
n 13
Labeling a flowchart(continued)
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n Prof. Shoukat Choudhury
n 14
Labeling a flowchart-continue
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n Prof. Shoukat Choudhury
n 15
Consistent on Notation
m = mass
! = mass flow rate
m
n = moles
! = molar flow rate
n
V = volume
! = volume flow rate
V
x = component fraction (mass or moles) in liquid
y = moles fraction in gas
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n Prof. Shoukat Choudhury
n 16
Example
4.2-‐3
Two
methanol
water
mixtures
are
contained
in
separate
flasks.
The
first
mixture
contains
40
wt%
methanol,
and
the
second
contains
70%
methanol.
If
200
g
of
the
first
mixture
is
combined
150
g
of
the
second,
what
are
the
mass
and
composiEon
of
the
product?
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n Prof. Shoukat Choudhury
n 18
Try This..
n Example 4.3.1
An experiment on the growth rate of certain organism
requires an environment of humid air enriched in oxygen.
Three input streams are fed into an evaporation chamber
to produce an output stream with the desired composition.
A: Liquid water fed at rate of 20 cm3/min
B: Air (21% O2 and 79% N2)
C: Pure O2 with a molar flow rate one-fifth of the molar
flow rate of stream B
The output gas is analyzed and is found to contain 1.5
mole% water. Draw and label the flowchart of the process,
and calculate all unknown stream variables.
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n Prof. Shoukat Choudhury
n 19
Solution
0.200n!1 mol O2/min
n! 3 mol/min
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n Prof. Shoukat Choudhury
n 20
Flowchart Scaling & Basis of Calculation
2 kg
0.5 kg C6H6/kg
1 kg C7H8
0.5 kg C7H8/kg
x 300
300 kg C6H6
600 kg
0.5 kg C6H6/kg
300 kg C7H8 0.5 kg C7H8/kg
kg kg/h
Replace kg with lbm
300 lbm/h
600 lbm/h
0.5 lbm C6H6/lbm
300 lbm/h 0.5 lbm C7H8/lbm
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n Prof. Shoukat Choudhury
n 22
Flowchart Scaling & Basis of Calculation
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n Prof. Shoukat Choudhury
n 23
Basis of Calculation
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n Prof. Shoukat Choudhury
n 24
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Flowchart
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n Prof. Shoukat Choudhury
n 40
K-salt Recovery
• In a steady state process crystalline potassium
chromate (K2CrO4) is recovered from an aqueous
solution of this salt.
• 10 ton per hour of a solution that is 30% K2CrO4 by
mass is fed into an evaporator. The concentrated
stream leaving the evaporator contains 50% K2CrO4 ;
this stream is fed into a crystallizer in which it is
cooled (causing crystals of K2CrO4 to come out of
solution) and then filtered. The filter cake consists of
K2CrO4 crystals and a solution that contain 35% K2CrO4
by mass; the crystals account for 95% of the total
mass of the filter cake. The filtrate drains out of the
system also contains 35% K2CrO4.
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n Prof. Shoukat Choudhury
n 41
10 ton per hour of a solution that is 30% K2CrO4 by mass is fed into an
evaporator. The concentrated stream leaving the evaporator contains 50%
K2CrO4 ; this stream is fed into a crystallizer in which it is cooled (causing
crystals of K2CrO4 to come out of solution) and then filtered. The filter cake
consists of K2CrO4 crystals and a solution that contain 35% K2CrO4 by mass; the
crystals account for 95% of the total mass of the filter cake. The filtrate drains
out of the system also contains 35% K2CrO4.
.
m1 kg W/h
Filter Cake
Fresh Feed . .
10,000 kg/h m2 kg/h
Crystallizer m3 kg/h
.
Evaporator & Filter m4 kg/h
0.30 kg K/kg 0.50 kg K/kg
0.70 kg W/kg 0.50 kg W/kg 0.35 kg K/kg
0.65 kg W/kg
Filtrate
. 0.35 kg K/kg
m 5 kg/h 0.65 kg W/kg
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n Prof. Shoukat Choudhury
n 42
m1 = 4000 kg W/h
m2 = 6000 kg K-soln/h
m3 = 1385 kg K(S)/h
m4 = 73 kg K-soln/h
m5 = 4542 kg K-soln/h
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n Prof. Shoukat Choudhury
n 43
K-salt Recovery
• In a steady state process crystalline potassium chromate (K2CrO4) is
recovered from an aqueous solution of this salt.
• 10 ton per hour of a solution that is 30% K2CrO4 by mass is joined
by a recycle stream containing 35% K2CrO4, and combined stream
is fed into an evaporator.
• The concentrated stream leaving the evaporator contains 50%
K2CrO4; this stream is fed into a crystallizer in which it is cooled
(causing crystals of K2CrO4 to come out of solution) and then
filtered.
• The filter cake consists of K2CrO4crystals and a solution that contain
35% K2CrO4 by mass; the crystals account for 95% of the total mass
of the filter cake. The solution that passes through the filter also
35% K2CrO4, is the recycle stream.
• Calculate the rate of evaporation, the rate of production of
crystalline K2CrO4, the feed rates that the evaporator and the
crystallizer must be designed to handle and the recycle ratio
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n Prof. Shoukat Choudhury
n 44
Product Separation & Recycling
.
m 2 kg W/h
Filter Cake
Fresh Feed . . .
m1 kg/h
10,000 kg/h m3 kg/h Crystallizer m4 kg/h
0.30 kg K/kg
Evaporator & Filter .
MP 0.50 kg K/kg
0.70 kg W/kg 0.50 kg W/kg m 5 kg/h
0.35 kg K/kg
0.65 kg W/kg
Recycle
.
m 6 kg/h
0.35 kg K/kg
0.65 kg W/kg
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n Prof. Shoukat Choudhury
n 45
Product Separation
& Recycling
n Without Recycle
m1 = 19662 kg mixed feed /h
m2 = 6900 kg Water evaporated/h m2 = 4000 kg W/h
m3 = 12762 kg fed to crystallizer/h m3 = 6000 kg K-soln/h
m4 = 2945 kg crystals/h m4 = 1385 kg K(S)/h
m5 = 155 kg K-soln/h m5 = 73 kg K-soln/h
m6 = 9662 kg recycle/h m6 = 4542 kg K-soln/h
Recycle Ratio= 0.9662 Kg recycle/Kg
Fresh feed
Comment:
Crystal production increases 113% due
to recycling
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n Prof. Shoukat Choudhury
n 46
Recycle and Bypass
n What is wrong here?
• Reuse of reactants/feed
• Recovery of catalyst
• Dilution of process streams (improve filter
operation)
• Control of a process variable (Reduce
reactant concentration)
• Circulation of a working fluid
(Refrigeration)
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n Prof. Shoukat Choudhury
n 47
Product Separation and Recycle
• Normally, reactions are not complete
– Separation and recycle
– Improved yield, conversion ,…
Reactants Product Products
Reactor Separation
Unit
Recycle
ü Process feed
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n Prof. Shoukat Choudhury
n 48
Balances on Reactive Systems
• Stoichiometry
The theory of proportions in which chemical
species combine with one another.
– Example: 2 SO2 + O2 à 2 SO3
• Stoichiometric Ratio
• Ratio of stoichiometric coefficients
– Example
2 mol SO3 produced 2 mol SO2 reacted
1 mol O2 reacted 2 mol SO3 produced
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n Prof. Shoukat Choudhury
n 49
Terminology
• Limiting reactants
Exist less than stoichiometric proportion
• Excess reactants
Exist more than stoichiometric proportion
• Example
2SO2 + O2 à 2 SO3
(30 mol) (10 mol)
Excess Limiting
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n Prof. Shoukat Choudhury
n 50
Terminology
n − ns
• Fractional excess n
s
• Percent excess n − ns
× 100
• Example ns
– H2 + Br2 à HBr
– H2 : 25 mol /hr
– Br2 : 20 mol /hr
– Fractional Excess H2 = (25 – 20 ) /20 = 0.25
– Percent Excess = 25 %
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n Prof. Shoukat Choudhury
n 51
Terminology
• Fractional conversion
– Chemical reactions are not always completed.
– Factional conversion
• f = (moles reacted) / (moles fed)
– When fresh feed consists of more than one
material the conversion must be stated for a
single component, usually the limiting
reactant.
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n Prof. Shoukat Choudhury
n 52
Terminology
reactant input to process - reactant output from process
Overall Conversions =
reactant input to process
reactant input to reactor - reactant output from reactor
Single-Pass Conversions =
reactant input to reactor
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n Prof. Shoukat Choudhury
n 55
A simple Problem
The oxidation of ethylene to produce
ethylene oxide proceeds as: 2 C2H4 + O2
= 2 C2H4O
The feed to the reactor contains 100 Kmol
C2H4 and 200 Kmol O2. What is the
limiting reactant? What is the percentage
excess of the other reactant? If the
reaction proceeds to a point where the
fractional conversion of the limiting
n reactant is 50%,Prof.how
3/29/15
n much
Shoukat Choudhury
of each 56
n
Multiple Reaction, Yield,
Selectivity
• Multiple reaction : one or more reaction
– Side Reaction : undesired reaction
– Example: Production of ethylene
C2H6 à C2H4 + H2
Side Reactions
C2H6 + H2 à 2CH4
C2H4 + C2H6 à C3H6 + CH4
– Design Objective
• Maximize desired products (C2H4)
• Minimize undesired products (CH4, C3H6)
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n Prof. Shoukat Choudhury
n 57
Terminology
moles of desired product formed
YIELD =
moles that would have been formed if there
were no side reactions and the limiting reactant
had reacted completely
moles of desired product formed
n Yield =
moles of reactant fed
moles of desired product formed
n Yield =
moles of reactant consumed
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n Prof. Shoukat Choudhury
n 58
Determination of yield and
Reaction: selectivity
C2H6 + 2.5O2 → 2CO +
3H2O
C2H6 + 3.5O2 → 2CO2
+3H2O
Undesired product: CO
100 mol C H
80% reactor
REACTOR conversion
Products
n
2 6
n 20 mol C2H6
500 mol O2
n 120 mol CO2
n 40 mol CO Yield = 0.6 or 1.2 or 1.5
n 240 mol O2
n 240 mol H2O Selectivity = 3.0
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n Prof. Shoukat Choudhury
n 59
Problem
Ethane is burned with air in a continuous
steady-state combustion reactor to yield a
mixture of carbon monoxide, carbon
dioxide, and water. The feed to the reactor
contains 10% C2H6. The percentage
conversion of ethane is 80%, and gas
leaving the reactor contains 8 mol CO2 per
mol of CO. Determine molar composition
n Reaction:
of productn Cgas.
2H6 + 5/2 O2 → 2CO + 3H2O
n C2H6 + 7/2 O2 → 2CO2 +3H2O
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n Prof. Shoukat Choudhury
n 60
Concept of Purge-
• Production of Ethylene Oxide
why needed?
• Reaction: 2C2H4 + O2 → 2C2H4O
• Mixture of Ethylene and air stream is charged to the reactor
• Reactor effluent is charged to absorber and gas stream
containing N2, O2 and unreacted ethylene is charged back to
reactor
Recycle
Products
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n Prof. Shoukat Choudhury
n 61
Production of Ethylene Oxide
• Problem: accumulation of N2
• Solution: allow purging of inert species
Recycle Purge stream
50 mol C2H4/s 10 mol C2H4/s
25 mol O2/s 5 mol O2/s
565 mol N2/s 113 mol N2/s
60 mol C2H4/s
Reactor 50 mol C2H4/s Absorber
100 mol C2H4/s
30 mol O2/s 50 mol C2H4O/s
50 mol O2/s
25 mol O2/s
113 mol N2/s 565 mol N2/s Products
565 mol N2/s
50 mol C2H4O/s
solvent
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n Prof. Shoukat Choudhury
n 62
Purging
Purging
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n Prof. Shoukat Choudhury
n 63
Definition
• A Recycle Stream is a term denoting a
process stream that returns material from
downstream of a process unit back to the
process unit.
• A Bypass stream - one that skips one or
more stages of the process and goes
directly to another downstream stage.
• A Purge stream – a stream bled off to
remove an accumulation of inert or
unwanted material that might otherwise
n build up in the recycle
3/29/15
n stream.
Prof. Shoukat Choudhury
64
n
Example 4.7-3, page 139
Recycle and Purge in the Synthesis of Methanol
Methanol is produced in the reaction of carbon dioxide and
hydrogen: CO2 + 3H2 → CH3OH + H2O
The fresh feed to the process contains hydrogen, carbon
dioxide and 0.40 mole percent inerts(I). The reactor effluent
passes to a condenser that removes essentially all of the
methanol and water formed and none of the reactants or
inerts. The latter substances are recycled to the reactor. To
avoid buildup of the inerts in the system, a purge stream is
withdrawn from recycle. The feed to the reactor contains
28.0 mole% CO2, 70 mole% H2 and 2% inerts. The single
pass conversion of H2 is 60%. Calculate the molar flow rates
and molar compositions of the fresh feed, the total feed to
the reactor, the recycle stream, and the purge stream for a
methanol production rate of 155 kmol methnol/hr.
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n Prof. Shoukat Choudhury
n 65
Reaction: CO2 + 3H2 → CH3OH + H2O
Basis: 155 kmol CH3OH/h
Recycle Purge
N8 kmol/h N7 kmol/h
x6C mol CO2/mol x6C mol CO2/mol
x6H mol H2/mol x6H mol H2/mol
(1-x6C-x6H) mol I/mol (1-x6C-x6H) mol I/mol
N6 kmol/h
x6C mol CO2/mol
x6H mol H2/mol
(1-x6C-x6H)mol I/mol
n1 kmol/h n2 kmol/h
REACTOR CONDENSER
x1C mol CO2/mol 0.28 mol CO2/mol n3 kmol CO2/mol
(0.996-x1C)mol H2/mol 0.70 mol H2/mol n4 kmol H2/mol
0.004 mol I/mol 0.02 mol I/mol n5 kmol I/mol
155 kmol CH3OH/h
155 kmol H2O/h 155 kmol CH3OH/h
155 kmol H2O/h
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n Prof. Shoukat Choudhury
n 66
Combustion Reaction
• Combustion
– A rapid reaction of a fuel with oxygen
– Fuels : coal, fuel oil, gas fuel, solid fuel, …
– Complete combustion / incomplete
combustion
– Wet basis composition / dry basis composition
Remember:
Orsat analysis yields dry basis composition
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n Prof. Shoukat Choudhury
n 67
Terminology
• Theoretical oxygen : Amount of oxygen
needed for complete combustion
– all carbon in the fuel is oxidized to CO2 and
– all the hydrogen is oxidized to H2O
• Theoretical air : The quantity of air that
contains theoretical oxygen
Air(theo) = 4.76 x O2(theo)
• Excess air : The amount by which the
air fed to reactor exceeds the
(moles air)fed − (moles air)theroretical
theoretical air (moles air )theoretical ×100%
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n Prof. Shoukat Choudhury
n 70
Questions
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n Prof. Shoukat Choudhury
n 71
Chemical Reaction
• What is final composition ?
ˆνi
– Chemical equilibrium
K = ∏ f i thermodynamics
K = ∏ aνi i
d ln K ΔH r
=
dT RT
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n Prof. Shoukat Choudhury
n 72
Sources of equations of unknown process
variables:
1. Material balances
2. An energy balance
3. Process specifications
4. Physical properties and laws
5. Physical constraints
6. Stoichiometric relations
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n Prof. Shoukat Choudhury
n 73
Variables in process design or analysis
– Temperature
– Pressure
– Flow rate
– Chemical composition
– Physical properties
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n Prof. Shoukat Choudhury
n 75
Topic Outcomes
• Given a process description:
– Draw and fully label a flowchart
– Choose a convenient basis of calculation
– For a multiple-unit process, identify the
subsystems for which balances might be
written
– Perform DoF analysis for the overall system
and each possible subsystems
– Write in order the equations you would use
to calculate specified process variables
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– Perform the calculations
Prof. Shoukat Choudhury
n 76
n
Topic Outcomes
• Do these computations
– for single-unit and multiple-unit processes and
– for processes involving recycle, bypass, or
purge streams
• If the system involves reactions, you
should be able to use
– molecular species balances,
– atomic species balances, or
– extents of reaction for both the DoF analysis
3/29/15
and the processProf.
n n calculations
Shoukat Choudhury
n 77
Topic Outcomes
• Given a combustion reactor and
information about the fuel composition
– calculate the feed rate of air from a given
percent excess or vice versa
• Given additional information about the
conversion of the fuel and the absence or
presence of CO in the product gas
– calculate the flow rate and composition of the
product gas
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n Prof. Shoukat Choudhury
n 78