1

Industrial Stoichiometry-II
DR. KHURAM MAQSOOD
NFC INSTITUTE OF ENGINEERING AND FERTILIZER RESEARCH, FAISALABAD
 2

Name of Course/
Module Industrial Stoichiometry II

Course Code ChE-201

Name of
Dr. Khuram Maqsood
Academic Staff
Rationale for the This course prepares the students to formulate and solve material and
inclusion of course energy balances on chemical process systems and lay the foundation for
in the program different subsequent courses. It also introduces the engineering approach
to solve process related problems.
Semester and year
offered 3/2

Credit Value 3
Prerequisite (if any)
Stoichiometry I
 3

Objectives 1. To introduce students with the calculation techniques used in

chemical engineering
2. To help them understanding material and energy balances
3. To learn the techniques of chemical engineering problem
solving
4. To offer practice in defining problems, collecting data,
analyzing the data and breaking it down into basic patterns
Learning At the end of this course, students should be able to:
Outcomes
1. Define and analyze the conservation equations for a given
process
2. Develop flow sheeting for different chemical process
3. Interpret available data and apply appropriate equations for
determination of flow rates, compositions and temperatures
in a process flow sheet
4. Perform material and energy balance calculations for a given
process
 4

Teaching-learning
and assessment 1. Coursework: 60% (Quizzes 20%, Assignments: 5%, attendance
strategy 5%, Mid 30%)
2. Examination (90 min): 40%

Synopsis Introduction to the Chemical Industry, Introduction to

Chemical Engineering Calculations, Techniques of
Problem Solving, Material Balance for Various System,
Energy Balance for Various Systems, Combined
Material and Energy Balance.
 5

Reference Books
Basic Principles and Calculations in Chemical Engineering, David M.
Eighth Edition Himmelblau
Elementary Principles of Chemical Processes, R. M. Felder
Third Edition R. W. Rousseau
Chemical Process Principles (Part 1), Second Edition Olaf A. Hougen
“Material & Energy Balance” K. M. Watson
R. A. Ragatz
Introduction to Material and Energy Balances G. V. Reklaitis
D. R. Schneider
Handbook of Chemical Engineering Calculations T. G. Hicks
N. P. Chopey

Both books at the top are main text books for this subject
Material and Energy Balances 6

1. Understanding and solving problems based on balance equations.

These concepts and solution techniques are used to determine the
distribution of material and energy flows in a chemical process.
2. Balance computations are based on the principles of conservation
of mass and energy.
3. Applying the balance equations to determine the flows,
compositions, and temperatures of all streams in a flowsheet.
Batch Process 7

 Feed is charged into a system. The system works on the feed until
processing is complete. Products are then removed.
 System is closed, with no material transfer across system boundaries
except during charging and product removal.
Examples are:
 Cooking
 Brewing
 Specialty chemicals
Continuous Process 8

 Feed and products flow continuously through process.

 System is open, and usually modeled as steady flow.
Examples are:
 Petroleum refining
 Fertilizer Plant
Semibatch Process 9

 Hybrid of batch and continuous.

 In one form ("fedbatch") the feed is added continuously, but the
product is removed all at once. Juice making
 In some cases (i.e. batch distillation), the feed is charged into the
vessel in one step, but the products are removed continuously
during the run.
 A uniform state open system model is one approach to these
problems.
Transient Models 10

 Also called "dynamic" or "unsteady state“

 Models are functions of time, so the system can track fluctuations
and changes in behavior
 These usually require differential equations
Steady State Models 11

 Also called "stationary" or "static" models

 Models do not change with time. This occurs when a dynamic
model achieves balance and all disturbances have attenuated, or
at some theoretical "long time" that represents the "normal" behavior
of the system.
 These can usually be modeled with algebraic equations.

Batch and semibatch processes require transient models

(they never reach a steady state). Continuous processes
may be modeled either as transient or as steady state.
General Balance Equation 12
(Applies to mass, components, energy, etc.)
General Balance Equation 13

 The system is any process or portion of a process chosen by the

engineer for analysis. A system is said to be "open" if material flows
across the system boundary during the interval of time being
studied; "closed" if there are no flows in or out.
 Accumulation is usually the rate of change of holdup within the
system -- the change of material within the system. It may be
positive (material is increasing), negative (material decreasing), or
zero (steady state).
 If the system does not change with time, it is said to be at steady
state, and the net accumulation will be zero.
 If there is no chemical reaction, the production and consumption
terms are typically zero.
Lecture Plan 14
 Introduction to material balance
 Solving material balances that involve chemical reactions.
Week 1  Calculation of excess air.
 Material balance for corrosion inhibitors in boilers.
 Combustion of methane rich biogas.
 Combustion of coal.
Week 2
 Solving material balance involving multiple subsystems.
 Multiple units in which no reaction occurs.
 Multiple units in which a reaction takes place.
 Recycle processes without chemical reactions.
Week 3
 Recycle in distillation process.
 Recycle in separation processes.
 Recycle in processes with chemical reactions.
 Calculation of overall fraction conversion.
Week 4
 Calculation of once-through fraction conversion.
 Bypass calculations.
 Bypass in process without chemical reaction.
 Bypass with chemical reaction.
Week 5
 Purge stream calculation.
 Calculation of purge stream in methanol synthesis process.
 Introduction to energy balance.
Week 6  General energy balance equation.
 Equation for closed system.
Lecture Plan... 15

• General energy balance equation for open system.

Week 7 • Calculation of enthalpy changes.
• Use of heat capacity equation.
• Tables of enthalpy values for the calculation of enthalpy
changes.
Week 8 • Graphical representation of enthalpy data.
• Application of the General Energy Balance to non-reactive
systems.
• Energy balance for closed system.
• Liquefaction of CO2 in cylinder by removing heat.
Week 9
• Energy balance for open system.
• Energy balance for fluid flow system.
• Energy balance for a reactor heating system.
• Energy balance that account for chemical reactions.
Week 10 • Basic information needed to accommodate reactions in
enthalpy calculations.
• Retrieval of heats of formation from reference data.
• Heat of formation for a compound in different phases.
• Heating value of coal.
Week 11
• Application of the energy balance to a process in which the
temperature of the entering and exit streams differ.
Lecture Plan… 16

• Reversible processes and the Mechanical Energy Balance equation.

• Calculation of reversible work for flow process.
Week 12 • Application of the Mechanical Energy Balance equation.

• Introduction to degree of freedom.

Week 13 • Determining the degree of freedom in a process.
• Proper process specifications.

• Degree of freedom with a reaction taking place in the system.

Week 14 • Degree of freedom for the case of multiple reactions.

• Degree of freedom in a system composed of several units.

Week 15 • Combined material and energy balance calculations over calcining
process.

• Steam system in a process.

Week 16 • Refinery process.
• Calculation of evaporator system.
 Material Balance Equation 17

C  O2  CO2
Accumulation = In - Out + Generation - Consumption

O2 0 = 1 - 0 + 0 - 1

Accumulation = In - Out + Generation - Consumption

C 0 = 1 - 1 + 0 0
O 0 = 2 - 2 + 0 0
 Material Balance Equation 18

C  O2  CO2
Accumulation = In - Out + Generation - Consumption

C 0 = 1 - 1 + 0 0
O2 0 = 1 - 1 + 0 0
Flue or stack gas: 19

All of the gases resulting from a combustion

process including the water vapor,
sometimes known as a wet basis.
Orsat analysis, or dry basis: 20

All of the gases resulting from a combustion

process not including the water vapor.
Complete combustion: 21

The complete reaction of the fuel

producing CO2 and H2O.
Partial combustion: 22

The combustion of the fuel producing at

least some CO from the carbon source, the
production of CO in a combustion process
does not produce as much energy as would
be the case if only CO2 were produced.
Theoretical air (or theoretical 23

oxygen):
The amount of air (or oxygen) required to
be brought into the process for complete
combustion. Sometimes this quantity is
called the required air (or oxygen).
Excess air (or excess oxygen): 24

Excess air (or oxygen) is the amount of air

(or oxygen) in excess of the theoretical air
required for complete combustion.

excess air excess O 2 / 0.21

% excess air  100  100
required air required O 2 / 0.21
Example 3.10 : Excess Air 25

Fuels for motor vehicles other than gasoline are being evaluated
because they generate lower levels of pollutants than does gasoline.
Compressed propane has been suggested as a source of power for
vehicles. Suppose that in a test 20 kg of C3H8 is burned with 400 kg of
air to produce 44 kg of CO2 and 12 kg of CO. What was the percent
excess air?
Sol:

C3H8 + 5O2 → 3CO2 + 4H2O

 26
The entering O2 is

The percentage excess air is

Example 3.12 : Combustion 27

Generation of methane-rich bio gas is a way to avoid high waste

disposal cost and burning it can meet upto 60% of operating cost for
such waste to energy plants. Further in European Community (EC) bio
gas plants are exempt from energy or carbon taxes, which will make
them more attractive if the EC enforces its carbon tax proposal. Four
full scale demonstration projects are now up and running in Europe. Let
us consider only the combustion of Methane. Figure shows a simple
combustion problem, the mechanical details of which we can ignore.

CH4=100%
Burner P = ? (kg moles)
F = 16.0 kg CO2 = ?
Air = mol% N2 = ?
A= 300kg O2 = 21% O2 = ?
N2 = 79% H2O = ?
 Sol: Element Balance 28
O  2  2.184 = 4.36 kg mole
Basis  16 kg CH 4
N  2  8.216 = 16.4 kg moles
Stream F
Stream P
16
CH 4   1 kg mole CO2  x1 kg moles
16
Element Balance O2  x 2 kg moles
C  1 kg mole N 2  x 3 kg moles
H  4 kg moles H 2O  x 4 kg moles
Stream A Element Balance
300 C = x1 kg moles
Air   10.40 kg moles
28.84 O  (2x1 +2x 2 +x 4 ) kg moles
O 2 in A  0.2110.40  2.184 kg moles N  2x 3 kg moles
N 2 in A  10.40  2.184  8.216 kg moles H  2x 4 kg moles
Overall Element Balance x1 = 1 kg mole 29
Accumulation  0 x 4 = 2 kg moles
Input  Output From Eq(2)
F AP
4.36 = 2(1) + 2 + 2x 2
C 1  0  x1 (1)
x 2 = 0.18 kg moles
O 0 + 4.36 = 2x1  2 x2  x4 (2)
From Eq(3)
N 0 + 16.46 = 2x 3 (3)
H 4 + 0 = 2x 4 (4) 2x 3 =16.46
x 3 = 8.23 kg moles
Analysis 30

Composition kg moles Mole %

CO2 1 8.76
O2 0.18 1.577
N2 8.23 72.12
H2O 2 17.54
Total P 11.41 100
Example 3.13: Combustion with Non Precise data 31

The main advantage of catalytic incineration of odorous gases or

obnoxious substances over direct combustion is the lower cost.
Catalytic incinerators operate at lower temperature – 500 to 9000C
compared with 1100 to 15000C for thermal incinerators and use
substantially les fuel. Because of the lower operating temperatures,
material of construction do not need to be heat resistance, reducing
installation and construction cost.
In a test run, a liquid that is propose for use as a fuel in a flare and has
the composition of 88% C and 12% H2 is vaporized and burned with dry
air to a flue gas (fg) of the following composition.
CO2 = 13.4%
O2 = 3.6%
N2 = 83%
To Help design the equipment of the continuous steady-state
combustion device, determine how many kilogram moles of dry fg are
produced per 100kg of liquid feed. What was the percentage of
excess air used.
 32

H2O = ?
W
F Catalytic G, Dry Flue Gas
Liquid Fuel Oxidation Unit CO2 = 13.4%
N2 = 3.6%
F = 100 kg Air = mol% O2 = 83%
C = 88 wt % A O2 = 21%
H2 = 12 wt % N2 = 79%
Basis, F = 100 kg
Stream F Stream G 33
88 CO 2 = 0.134G kg moles
C= =7.33 kg moles
12 O 2 = 0.036G kg moles
12 N 2 = 0.83G kg moles
H2 = = 6 kg moles
2 Element Balance
Element Balance C = 0.134 kg moles
C = 7.33 kg moles O = 2  0.134G + 2×0.036G = 0.34G kg moles
H = 12 kg moles N = 2×0.83G = 1.66G kg moles
Stream A Stream W
O 2 =0.21A kg moles H 2 O = W kg moles
N 2 = 0.79A kg moles Element Balance
Element Balance O = W kg moles
O = 2×0.21A = 0.42A kg moles H = 2W kg moles
N = 2×0.79A =1.58A kg moles
 34
Overall Element Balance
Accumulation  0
Input  Output
F  A  G W
C 7.33 + 0 = 0.134G + 0 (1)
H 12 + 0 = 0 + 2W (2)
O 0 + 0.42A = 0.34G + W (3)
N 0 + 1.58A = 1.66G + 0 (4)
From Eq (1)
35
7.33 = 0.134G
G = 54.70 kg moles
From Eq (2)
12 = 2W
W = 6 kg moles
From Eq (3)
0.42A = 0.34 (54.70) + 6
A = 58.566 kg moles
 kg moles of dry flue gas
(A)  54.70 kg moles
100 kg of fuel burned 36
(B) Excess Air
Component Reaction kg moles O 2 Re quired
C C +O 2  CO2 7.33 7.33
1 6
H H 2 + O2  H 2O =3 3
2 2
10.33
Total

O 2 Supplied in A = 0.21A = 0.21  58.57 = 12.2997 kg moles

O 2 supplied - O 2 required 12.2997  10.33
% excess air = 100  100
O2 Required 10.33
= 19.06 %
Assignment 37

 Problem 06, Self assessment exercise, Section 3.4. 6th Edition

Example 3.14: Combustion of Coal 38

A local utility burns coal having the following composition on a dry

basis. (Note that the coal analysis below is a convenient one for our
calculations, but is not necessarily the only type of analysis that is
reported for coal. Some analyses contain much less information about
each element.)

Component Percent
C 83.05
H 4.45
O 3.36
N 1.08
S 0.70
Ash 7.36
Total 100
Example 3.14 39
The average Orsat analysis of the gas from the stack during a 24-hr test
was
Component Percent
CO2 + SO2 15.4
CO 0
O2 3.36
N2 80.6
Total 100

Moisture in the fuel was 3.90%, and the air on the average contained
0.0048 lb H2O/lb of dry air. The refuse showed 14.0% unburned coal,
with the remainder being ash.
You are asked to check the consistency of the data before they are
stored in a data base. Is the consistency satisfactory? What was the
average percent excess air used?
 H2O(g) = 100% 40
lb
C = 83.05 W (lb mol)
H = 4.45
O = 3.36 CO2 + SO2 = 15.4 %
N = 1.08 O2 = 4.0 %
S = 0.70 Coal Stack gas N2 = 80.6 %
CO = 0.0 %
Ash = 7.36 Furnace
100.0 F (lb) P (lb mol)

H2O = 3.90 lb Air A (lb mol)

H = 0.433 lb mol Refuse R lb
Containing: Mol fr:
N2 = 0.79 R
O2 = 0.21 C+H+O+N+S = 14%
O = 0.217 lb mol Ash = 86%
1.0
H2O = 0.0048 lb/lb air
H = 0.0154 lb mol/lb mol A
Containing:
O= 0.0077 lb mol/lb mol A
Sol: 41

Reactions
C  O2  CO2
S  O2  SO2
1
H 2  O2  H 2O
2
Basis, F = 100 lb of Coal
Stream F 42

Component Mass (lb) lb moles

C 83.05 6.921
H 4.45 4.450
O 3.36 0.210
N 1.08 0.0771
S 0.70 0.0219
Ash 7.36 -
Stream R 43
By Ash Balance
Ash in F = Ash in R
7.36 = 0.86R
R = 8.558 lb
Unburned Coal in R = 8.558  0.14 = 1.198 or 1.20 lb
 Assuming the same composition of components in F and R
44
Component Mass %age Mass %age on lb lb moles
in F ash free basis
(lb)
C 83.05 83.05 0.8964x1.20 = 1.075 1.075/12 = 0.089
x100=89.64
(100−7.36)

H 4.45 4.45 0.0480x1.20 = 0.0576 0.0576/1 = 0.0576

x100=4.80
(100−7.36)

3.36
O 3.36 x100=3.62 0.0362x1.20 = 0.04344 0.04344/16 = 0.003
(100−7.36)

1.08
N 1.08 x100=1.165 0.01165x1.20 = 0.01398 0.01398/14 = 0.001
(100−7.36)

0.70
S 0.70 x100=0.775 0.00775x1.20 = 0.0093 0.0093/32 = 0.0003
(100−7.36)

Total 0.1476
Carbon Balance
45
C in F = C in R + C in P
C in P = C in F - C in R
= 6.921 - 0.089 = 6.83 lb moles
Sulfur Balance
S in F = S in R + S in P
S in P = S in F - S in R
= 0.0219 - 0.0003 = 0.02187 lb moles
SO 2 in P = 0.02187 lb moles
CO 2 + SO 2 in P = 6.83 + 0.02187 = 6.852 lb moles
From CO 2 and SO 2 lb moles
0.154 P = 6.852 46
P = 44.49 lb moles
O 2 = 0.04  44.49 = 1.797 lb moles
N 2 = 0.806  44.49 = 35.85 lb moles
N = 2  35.85 = 71.7 lb moles
Stream A
N in A = N in R + N in P - N in F
= 0.001 +71.7 - 0.077 = 71.62 lb moles
71.62
N 2 in A =  35.81 lb moles
2
35.81
Total A =  45.32 lb moles
0.79
O 2 in A = 45.32  0.21 = 9.517 lb moles
 47

Component Reaction lb moles O2 Required (lb

moles)
C 𝐶 + 𝑂2 → 𝐶𝑂2 6.92 6.92

H 4𝐻 + 𝑂2 → 𝐻2𝑂 4.45 4.45

= 1.1125
4
S 𝑆 + 𝑂2 → 𝑆𝑂2 0.022 0.022

O - 0.21 −0.21
= −0.105
2
Total Required O2 7.9495
 48
O 2 Entering - O 2 Required
% excess air = 100
O 2 Required
9.517 - 7.9495
= 100 = 19.72%
7.9495
Problem 13 49
A hydrocarbon fuel in burnt with excess air. The Orsat analysis of the
flue gas shows 10.2% CO2, 1.0% CO, 8.4% O2, and 80.4% N2. What is the
atomic ratio of H to C in the fuel?

W H2O = ?

F P Mol %
Combustion CO2 = 10.2%
Fuel
H =x CO =1%
C=y Air = mol% N2 = 80.4%
A O2 = 21% O2 = 8.4%
N2 = 79%
𝐻
= ? In Fuel
𝐶
Soln: 50
Reactions
C  O2  CO2
1
C  O2  CO
2
1
2 H  O2  H 2O
2
Basis,
100 kg moles of P
Stream P
CO 2 = 10.2 kg moles
51
CO = 1.0 kg mole
O 2 = 8.4 kg moles Stream F
N 2 = 80.4 kg moles H = x kg moles
Element Balance C = y kg moles
C = 10.2 + 1.0 = 11.2 kg moles Stream W
O = 2 × 10.2 + 1.0 + 2 × 8.4 = 38.2 kgmoles H 2 O = W kg moles
N = 80.4  2 = 160.8 kg moles Element Balance
Stream A O = W kg moles
O 2 =0.21A kg moles H = 2W kg moles
N 2 = 0.79A kg moles
Element Balance
O = 2×0.21A = 0.42A kg moles
N = 2×0.79A =1.58A kg moles
 52
Overall Element Balance
Accumulation  0
Input  Output
F  A W  P
C y + 0 = 0 + 11.2 (1)
H x + 0 = 2W + 0 (2)
O 0 + 0.42A = W + 38.2 (3)
N 0 + 1.58A = 0 + 160.8 (4)
From Eq (1)
y = 11.2 53
From Eq (2)
x = 2W (5)
From Eq (4)
A = 101.772
From Eq (3)
0.42 (101.772) - 38.2 = W
W = 4.544 kg moles
From Eq (5)
x = 2  4.544 = 9.088 kg moles
H x 9.088
   0.811
C y 11.2
Example 3.16: Multiple Units without Reaction 54

Acetone is used in the manufacture of many

chemicals and also as a solvent. In its latter role, many
restrictions are placed on the release of acetone
vapor to the environment. You are asked to design an
acetone recovery system having the flowsheet
illustrated in Figure. All of the concentrations shown in
Figure of both the gases and liquids are specified in
weight percent in this special case to make the
calculations simpler. Calculate A, F, W, B, and D in
kilograms per hour. Assume that G = 1400 kg/hr.
 A, kg D, kg
Water, 100 % Air = 0.995
Condenser 3
55
Water = 0.005 Distillate
W, kg 1.0
Acetone = 0.99
Water = 0.01
1.0

Absorber Distillation B, kg
Column Column
Acetone = 0.04
Water = 0.96
1 2 1.0

G = 1400 kg/hr Acetone = 0.19

Entering Gas Water = 0.81
Air = 0.95 1.0
F, kg
Acetone = 0.03
Water = 0.02
1.0
Calculate A, F, W, B and D
Basis: 1 hr of operation
Stream G 56
Air = 0.95  1400 = 1330 kg
Acetone = 0.03  1400 = 42 kg
H 2 O = 1400 - (1330 + 42) = 28 kg
System 1 Absorber Column (1)
Accumulation = Input - Output + Generation + Consumption
For Steady State Conditions G+W=A+F (1)
Input = Output
Air Balance
1330 + 0 = 0.995 A + 0 (2)
Acetone Balance
42 + 0 = 0 + 0.19 F (3)
A = 1336.7 kg
F = 221.05 kg
W = 157.75 kg
System 2 Distillation Column (2) + Condenser (3)
57
For Steady State Conditions
Input = Output
F=D+B (4)
Acetone Balance
0.19 F = 0.99 D + 0.04 B (5)
D = 34.89 kg
F=D+B
B=F-D
B = 221.05 - 34.897 = 186.15 kg
 Example 3.17: Multiple Units with Reactions 58
In the face of higher fuel costs and the uncertainty
of the supply of a particular fuel, many companies
operate two furnaces, one fired with natural gas
and the other with fuel oil. In the RAMAD Corp.,
each furnace has its own supply of oxygen; the oil
furnace uses as a source of oxygen a stream that
has the following composition: O2 20%, N2 76%, and
CO2 4%. The stack gases from both furnaces exit
using a common stack.
During one blizzard, all transportation to the RAMAD Corp. was cut off, and
officials were worried about the dwindling reserves of fuel oil because the 59
natural-gas supply was being used at its maximum rate possible. The
reserve of fuel oil was only 560 bbl. How many hours could the company
operate before shutting down if no additional fuel oil was attainable? How
many pound moles per hour of natural gas were being consumed? The
minimum heating load for the company when translated into the stack gas
output was 6205 lb mol/hr of dry stack gas. Analysis of the fuels and stack
gas at this time is shown in Table. The molecular weight of the fuel oil was
7.91 lb/lb mol, and its density was 7.578 lb/gal.

Natural Gas Fuel Oil ( API Gravity =24.0) Stack Gas

Mol % (Orsat Analysis)
CH4 96% C 50 N2 84.93%
C2H2 2% H2 47 O2 4.13%
CO2 2% S 3 CO2 10.84%
SO2 0.10%
 Stack Gas Water
P = 6205 lb mol/hr W = 100% H2O 60
N2 = 84.93%
O2 = 4.13%
SO2= 0.10%
CO2=10.84% Air
100% O2 = 0.20
N2 = 0.76
CO2 = 0.04
1.0
A A*
Gas Oil
Air = mol% Furnace Furnace
O2 = 21%
N2 = 79%
100% Nat. Gas Fuel Oil
CH4 = 0.96 mol fr C = 0.5 mol fr
G C2H2 = 0.02 mol fr H2 = 0.47 mol fr
Fuel Oil Mol Wt = 7.91lb / lb mol
Density = 7.578 lb/gal
CO2 = 0.02 mol fr S = 0.03 mol fr
1.0 1.0
F
Sol: 61

CH 4  2O2  CO2  2 H 2O
5
C2 H 2  O2  2CO2  H 2O
2
C  O2  CO2
1
H 2  O2  H 2O
2
S  O2  SO2
Basis : 1 hr of operation
Stream P
62
P = 6205 lb moles
N 2 = 0.8493  6205 = 5270 lb moles
O 2 = 0.0413  6205 = 256.30 lb moles
SO 2 = 0.001  6205 = 6.21 lb moles
CO 2 = 0.1084  6205 = 672.40 lb moles
Element Balance
N = 2  5270 = 10540 lb moles
O = 2  256.30 + 2  6.21 + 2  672.40 = 1869.74 lb moles
S = 6.21 lb moles
C = 672.40 lb moles
Stream W Stream A
H 2 O = W lb moles O 2 = 0.21 A lb moles 63
Element Balance N 2 = 0.79 A lb moles
H = 2 W lb moles Element Balance
O = W lb moles O = 2  0.21 A = 0.42 A lb moles
Stream A* N = 2  0.79 A = 1.58 A lb moles
O 2 = 0.20 A* lb moles
N 2 = 0.76 A* lb moles
CO 2 = 0.04 A* lb moles
Element Balance
O = 2  0.20 A* + 2  0.04 A* = 0.48 A* lb moles
N = 2  0.76 A* = 1.52 A* lb moles
C = 0.04 A* lb moles
 64
Stream F Stream G
C = 0.50 F lb moles CH 4 = 0.96 G lb moles
C2 H 2 = 0.02 G lb moles
H 2 = 0.47 F lb moles
CO 2 = 0.02 G lb moles
S = 0.03 F lb moles Element Balance
Element Balance C = 0.96 G + 2  0.02 G + 0.02 = 1.02 G lb moles
C = 0.50 F lb moles H = 4  0.96 G + 2  0.02 G = 3.88 G lb moles
O = 2  0.02 G lb moles
S = 0.03 F lb moles
H = 2  0.47 F = 0.94 F
Overall Element Balance 65
A+G+F+A*=P+W
H 0 + 3.88 G + 0.94 F + 0 = 0 + 2 W (1)
O 0.42 A + 0.04 G + 0 + 0.48 A* = 1869.74 + W (2)
N 1.58 A + 0 + 0 + 1.52 A* = 10540 + 0 (3)
S 0 + 0 + 0.03 F + 0 = 6.21 (4)
C 0 + 1.02 G + 0.50 F + 0.04 A* = 672.40 + 0 (5)
From Equation (4)
66
0.03 F = 6.21
F = 207 lb moles
Put in Eq (1)
3.88 G + 0.94 (207) = 2 W
W = 1.94 G + 97.29 (6)
From Eq (3)
1.58 A + 1.52 A* = 10540
10540 - 1.52 A*
A=  6670.8  0.96 A * (7)
1.58
Put W and A from Eq (6) and (7) in Eq (2)
0.42 (6670.8 - 0.96 A*) + 0.04 G + 0.48 A* = 1869.74 + (1.94 G + 97.29) 67
A* = 24.73 G - 10901.05
From Eq (5)
1.02 G + 0.50 (207) + 0.04 (24.73 G - 10901.5) = 672.40
G = 500 lb moles (Answer of Part b)
Part a
207 lb moles 7.91 lb gal 1 bbl
hr lb moles 7.578 lb 42 gal
= 5.14 bbl / hr
For 560 bbl
𝟓𝟔𝟎
𝒕= = 108.9 hrs
𝟓.𝟏𝟒
Sec 3.5, Self Assessment Exercise, 9.2 68

A simplified process for the production of SO3 to be used in

the manufacture of sulfuric acid is illustrated in the Figure.
Sulfur is burned with 100 % excess air in the burner, but for
the reaction 𝑺 + 𝑶𝟐 → 𝑺𝑶𝟐, 90% conversion of the S to SO2 is
achieved. In the converter, the conversion of SO2 to SO3 is
95% complete. Calculate the lb of air required per 100lb of
sulfur burned, and the concentration in mole fraction of the
components in the exit gas from the burner and from the
converter.
 69
P1
SO2 = x1
Air = mol% O2 = x2
O2 = 21% N2 = x3
N2 = 79%
100%
Air, A
Burner Converter P2
90 % 95 %
F, Sulfur SO2 = x4
2 SO3 = x5
1 O2 = x6
N2 = x7

T S, Unburned
Reactions
90%
S+O 2  SO2 (i) 70
1 95%
SO2  O2  SO3 (ii)
2
Basis, F = 100 lb
Stream F
100
F=  3.125 lb moles
32
From Reaction (i)
O 2 Required = 3.125 lb moles
O 2 Supplied = 3.125 + 100% (3.125) = 6.25 lb moles
6.25
Air Supplied =  29.76 lb moles
0.21
N 2 Supplied = 29.76 - 6.25 = 23.51 lb moles
29.76 lb moles 28.84 lb
lb of Air Supplied =  = 858.27 lb
1 lb moles
Part a
lb of Air Supplied
 858.27 lb 71
100 lb of Sulfur Burned
System 1 (Burner)
Input - Output + Generation -Consumtion = 0
S 3.125 - T + 0 - (0.9  3.125) = 0
T = 0.3125 lb moles (1)
1
O2 6.25 - x 2 + 0 - (  0.90  3.125 ) = 0
1
6.25 - x 2 + 0 - 2.8125 = 0 (2)
N2 23.51 - x 3 + 0 - 0 = 0 (3)
1
SO 2 0 - x1 + (0.9  3.125 ) - 0 = 0 (4)
1
2
 x 2 = 3.4375 lb moles
3
 x 3 = 23.51 lb moles
4
 x1 = 2.8125 lb moles
System 2 (Converter)
Input - Output + Generation -Consumtion = 0 72
SO 2 x1 - x 4 + 0 - 0.95 x1 = 0 (5)
1
SO3 0 - x 5 + (0.95)x1 - 0 = 0 (6)
1
1/ 2
O2 x2 - x6 + 0 - (0.95)x1 = 0 (7)
1
N2 x3 - x7 + 0 - 0 = 0 (8)
8
 x 7 = 23.51 lb moles
5
 x 4 = 0.1406 lb moles
6
 x 5 = 2.671 lb moles
7
 x 6 = 2.101 lb moles
Part b 73
Stream P1
Component lb moles Mol%
SO2 2.81 9.44
O2 3.44 11.56
N2 23.51 79
Total 29.76 100
Stream P2
Component lb moles Mol%
SO2 0.1406 0.49
SO3 2.671 9.39
O2 2.101 7.39
N2 23.51 82.72
Total 28.42 100
Recycle Stream 74

Recycle stream is a term denoting a process

stream that returns material from downstream of a
process unit back to the process unit.
Bypass Stream 75

Bypass stream is a stream that skips one or

more stages of the process and goes directly
to another downstream stage.
Purge Stream 76

Purge stream is a stream bled off to remove

an accumulation of inerts or unwanted
material that might otherwise build up in the
recycle stream.
Example 3.18: Recycle without Chemical Reaction 77

A distillation column separates 10,000 kg/hr of a

mixture containing equal mass of benzene and
toluene. The product D recovered from the
condenser at the top of the column contains 95%
benzene, and the bottom W from the column
contains 96% toluene. The vapor V entering the
condenser from the top of the column is 8000
kg/hr. A portion of the product from the condenser
is returned to the column as reflux R, and the rest
is withdrawn as the final product D. Assume that V,
R, and D are identical in composition since V is
condensed completely. Find the ratio of the amount
refluxed R to the product withdrawn D.
78
 Sol:R 79
Calculate
D
Basis : 1 hr of Operation
From Eq (3)
System 1 (Process) R = 8000 - D
Accumulation = Input - Output + Generation - Consumption Putting Eq (1) in Eq (2)
Stream Balance 5000 = 0.95 D + 0.04 (10000 - D)
F=D+W D = 5054.95 kg
D = 10000 - W (1) R = 8000 - 5054.95
Benzene Balance = 2945.05 kg
0.5  10000 = 0.95 D + 0.04 W (2) W = 10000 - 5054.95 = 4945.05 kg
System II (Condenser + Splitter) R 2945.05
Input = Output   0.58
D 5054.95
8000 = D + R
Example 3.19 : Recycle without Chemical Reaction 80

Please Do it yourself
Example 3.20: Recycle with Chemical Reaction 81

Immobilized glucose isomerase is used as a catalyst in

producing fructose from glucose in a fixedbed reactor
(water is the solvent). For the system shown in Figure, what
percent conversion of glucose results on one pass through
the reactor when the ratio of the exit stream to the recycle
stream in mass units is equal to 8.33? The reaction is

C12 H 22O11  C12 H 22O11

 System I: Overall Balance
82

G = 0.40
W = 0.60 System II System III
1.0 Fixedbed P
T
S Reactor
CP,G
Mixer CT,G Splitter
CP,F
CT,F = 0.04
CP,W
CT,W
 Sol: 83

P
 8.33 (A) Fructose Balance
R
Basis, S  100 kg 0 + C P , F  R = 0.04 T (4)
System I (Overall Process) Glucose Balance
SP 0.4  100 + C P ,G  R  CT ,G  T (5)
P  100 (1) System III (Reactor + Splitter)
H 2 O Balance Input - Output + Generation - Consumption = Accumulation
0.60  100 = C P ,W  P (2) Glucose Balance
System II (Mixer) CT ,G  T  CP ,G  ( P  R )  0  f (CT ,G  T )  0 (6)
Input = Output
Stream Balance
S+R=T
100 + R = T (3)
Summation Equations
Stream T
84
5
CT ,G  0.04  CT ,W  1.0 (7)  40  0.027 12  CT ,G 112, CT ,G  0.36
5
Stream P
 0.360 112  0.027  (100  12)  f (0.36 112)
C P ,G  CP , F  CP ,W  1.0 (8)
40.32 - 3.024 - = f (40.32)
2
 CP ,W  0.6 f = 0.925 or 92.5%
A 100
R   12 kg
8.33
3
100  R  T , T  100  12  112kg
4
 CP , F  12  0.04  112, C P , F  0.373
8
 CP ,G  0.373  0.6  1, C P ,G  0.027
Example 3.21: Recycle with Chemical Reaction 85

Refined sugar (sucrose) can be converted to

glucose and fructose by the inversion process
C12H22O11 + H2O =======> C6H12O6 (G) + C6H12O6 (F)

The combined glucose and fructose is called

inversion sugar. If 90% conversion of sucrose
occurs on one pass through the reactor, what
would be the recycle stream flow per 100 lb fresh
feed of sucrose?
What is the concentration of inversion sugar in the
recycle and product streams? Assume that the two
streams are identical in composition. Refer to the
flowchart for the other details of the process.
 CR,S 86
CR,I
CR,W R

CF,S = 0.30
CF,W = 0.70 System II System III
1.0 P
Fˊ Reactor
F = 100 lb
Mixer CFˊ,S Splitter
CFˊ,I
CFˊ,W
 Sol: 87

Reaction
90% I = Inversion Suger =360
C12 H 22O11  H 2O  C6 H12O6  C6 H12O6
(342) 18
180 180

1 lbmole of Inversion 1 lbmole of sucrose 360 lb of inversion

sugar sugar = 1.052 lb of
inversion sugar / lb
of sucrose
I lbmole of Sucrose 342 lb of sucrose 1 lbmole of inversion
sugar
Basis
F  100lb 88
System I (Process)
Input = Output
F=P
100 = P (1)
Stream Balance
100 + R = F/ (2)
Inversion Suger balance
0 + CR,I  R = 0.05  F/ (3)
Sucrose Balance
0.30  100 + R  C R,S = C F/ , S  F/ (4)
System III (Reactor + Splitter) 89
Input - Output +Generation - Consumption = Accumulation
Sucrose Balance
0.05  F/  C R,S  (R + P) + 0 - 0.90 (C F/ , S  F/ ) (5)
Inversion Suger Balance
0.05  F/ - C R,I  (R + P) + 0.90 (C F/ , S  F/ ) 1.052 (6)
Summation Equation
/
Stream F
CF/ , S  0.05  CF/ ,W  1.0 (7)
Stream R 90
CR , S  CR , I  CR ,W  1.0 (8)
From Equation (3)
C R , I  R  0.05 F /
0.05 F /
CR , I 
R
From Equation (2)
F/  100  R
0.05(100  R) 5  0.05 R
CR , I   (9)
R R
From Equation (4)
30  R  CR , S  CF / , S  F / 91

CF / S  F /  30
CR , S  (10)
R
Put the values of P and C R , S from Eq (1) and (10)
(C F / , S  F / )  CF / , S  F /  30( R  100)  0.9(CF / , S  F / )  0
(CF / , S  F /  30)( R  100)
(CF / , S  F / )   0.90(CF / , S  F / )  0
R
(CF / , S  F / ) R  (CF / , S  F /  30)( R  100)  0.90(CF / , S  F / ) R  0
0.1(CF / , S  F / ) R  (CF / , S  F / ) R  100(CF / , S  F / )  30 R  3000  0
(0.1  1)(CF / , S  F / ) R  100(CF / , S  F / )  30 R  3000  0
0.9(CF / , S  F / ) R  100(CF / , S  F / )  30 R  3000  0
0.9(CF / , S  F / ) R  100(CF / , S  F / )  30 R  3000  0
(0.9 R  100)(CF / , S  F / )  30 R  3000 92
30 R  3000
CF / , S  F 
/

0.9 R  100
Put C R , I from eq (9) and F / from eq (2) to eq (6)
(5  0.05 R)  3000  30 R 
0.05(100  R)  ( R  100)  0.90 1.052 
R  100  0.9 R 
5  0.05 R 28.421
0.05   0
R 100  0.9 R
0.05 R(100  0.9 R)  (5  0.05 R)(100  0.90 R)  28.421R  0
5 R  0.045 R 2  500  4.5 R  5 R  0.045 R 2  28.421R  0
28.421R  4.5 R  500
(a) R = 20.902 lbmoles/hr
Put the values of R in eq (9)
93
5  0.05 R 5
CR , I    0.05
R R
5
CR , I   0.05
20.902
(b) CR , I  0.29
Example 3.23 (Bypass Calculations)
In the feedstock preparation section of a plant manufacturing natural 94
gasoline, isopentane is removed from butane-free gasoline. Assume for
purposes of simplification that the process and components are as
shown in Figure. What fraction of the butane-free gasoline is passed
through the isopentane tower? Detailed steps will not be listed in the
analysis and solution of this problem. The process is in the steady state
and no reaction occurs.
Sol: 95
From eq (1)
X
? S = 11.11 kg
F
Basis  100kg System II (Iso Pentane Tower)
System I (Process) Stream Balance
Stream balance X=Y+S (3)
F=P+S i-C5 H12 Balance
100 = P + S (1) 0.02 X = 0 + 11.11
11.11
n-C5 H12 Balance X=  55.55 kg
0.20
0.8  100 = 0.9  P + 0 (2)
X 55.55
P = 88.88 kg   0.555
F 100
 Example 3.23 (Purge) 96

Considerable interest exists in the conversion of coal into more convenient

liquid products for subsequent production of chemicals. Two of the main gases
that can be generated under suitable conditions from in situ (in the ground)
coal combustion in the presence of steam (as occurs naturally in the presence
of groundwater) are H2 and CO. After cleanup, these two gases can be
combined to yield methanol according to the following equation:
CO + 2H2 → CH3OH
Figure illustrates a steady-state, open process for the production of methanol.
All of the compositions are in mole fractions or percent. The stream flows will be
in moles. You will note in Figure E6.9a that some CH4 enters the process.
However, the CH4 does not participate in the reaction. A purge stream is used
to maintain the CH4 concentration in the exit stream from the separator going
to R and P at no more than 3.2 mol %, and to prevent H2 from accumulating in
the system. The once-through conversion of the CO in the reactor is 18%.
Compute the moles of recycle, R, the moles of CH3OH, E, and the moles of
purge, P, per 100 moles of feed, and also compute the purge gas composition.
 System I Overall Process 97

System II
Mole %
H2 = 67.3
CO = 32.5
Feed, F CH4 = 0.2
E
Reactor Separator
CH3OH = 100%
1 Mole 2
H2 = x
CO = y
Recycle, R CH4 , z = 0.032 Purge, P
 Sol: 98
R, P, E = ? Stream F
CO + 2H 2  CH 3OH Element Balance
Basis, F = 100 moles C = 0.2 + 32.5 = 32.7 moles
Sysytem I (Overall Process) H = 2  67.3 + 4  0.2 = 135.4 moles
H 2  67.3moles O = 32.5 moles
Stream E
CO  32.5moles
C = E moles
CH 4  0.2moles
H = 4 E moles
Input = Output
O = E moles
Stream P Stream P 99
H 2  x  P moles C 32.7 = E + (y +0.032)  P (1)
CO = y  P moles H 135.4 = 4 E + (2x + 0.128)  P (2)
CH 4 = 0.032  P molesO 32.5 = E + y  P (3)
Element Balance System II (Mixer + reactor + separator + splitter)
C = (y + 0.032)  P moles
Input - ourput + Generation - Consumption = Acuumu
H = (2x + 0.128)  P moles
CO balance
O = y  p moles (32.5 + y  R) - y (P + R ) + 0 - 0.18 (32.5 + y  R) =
Input = Output Summation Equation
F=E+P x + y + 0.032 = 1
Stream P
C 32.7 = E + (y +0.032)  P (1) 100

H 135.4 = 4 E + (2x + 0.128)  P (2)

O 32.5 = E + y  P (3)
System II (Mixer + reactor + separator + splitter)
Input - ourput + Generation - Consumption = Acuumulation
CO balance
(32.5 + y  R) - y (P + R ) + 0 - 0.18 (32.5 + y  R) = 0 (4)
Summation Equation
x + y + 0.032 = 1 (5)
5
 y = 0.968 - x (6)
Subtracting Eq (3) from Eq (1)
32.7 = E + y  P +0.032  P (1) 101
32.5 = E  y  P (3)


0.2 = 0.032  P
P = 6.25 moles
3
 32.5 = E + (0.968 - x)  6.25
26.45 = E - 6.25 x
Multiply with 2
52.9 = 2 E - 12.5 x (A)
2
 135.4 = 4 E + (2x +0.128)  6.25
134.6 = 4 E + 12.5x (B)
Adding Eq (A) and Eq (B)
52.9 = 2 E - 12.5 x (A) 102
134.6 = 4 E + 12.5x (B)


187.5 = 6 E
E = 31.25 moles
3
 32.5 - 31.25 = y (6.25)
y = 0.2
6
 x = 0.968 - 0.2
x = 0.768
4
 (32.5 + 0.2 R) - 0.2 (6.25 + R) - 0.18 (32.5 + 0.2 R) = 0
25.4 - 0.036 R = 0
R = 705.5 moles
 103

Thank you