Final Year Design Project Thesis Report Session 2018

Production Of 100 MTPD Of Epoxy Propane
Using Propene and Oxygenated Water by

HPPO Process
Session: 2018-2022
Muhammad Hafeez Rasheed 2018-CH-01

Syed Moazzam Ali 2018-CH-15
Muzzamil (Group Leader) 2018-CH-35
Ali Haider 2018-CH-36
Project Advisor
Engr. Mehboob Ahmad Aadil
Department of Chemical Engineering & Technology

Muhammad Nawaz Sharif University of Engineering and
Technology, Multan.
Final Year Design Project Report
Production Of 100 MTPD Of Epoxy Propane

Using Propene and Oxygenated Water by
HPPO Process
Session: 2018-2022
Muhammad Hafeez Rasheed 2018-CH-01

Syed Moazzam Ali 2018-CH-15
Muzzamil (Group Leader) 2018-CH-35
Ali Haider 2018-CH-36
Department of Chemical Engineering & Technology

MNS University of Engineering and Technology, Multan.
In the name of aLLah, the most
GracIous, the most mercIfuL

Summary
Propylene oxide is frequently employed as a chemical intermediary in the synthesis of

numerous compounds, including polyether polyols, propylene glycol and propylene glycol
ethers. Additionally, polyether polyol (polymeric polyol) is used to make polyurethane
foams, which is the main raw material used in the production of flexible foams for car
seats, home furniture and rigid foams used for insulation in buildings and construction.
Propylene glycol is used to make unsaturated polyester resins, cosmetics, antifreezes, and
pharmaceuticals, while propylene glycol ethers are used in the production of paints,
solvents, and coatings. Although there are other processes to make propylene oxide, the
hydrogen peroxide process is the one that is most frequently employed in industries. In this
design report, hydrogen peroxide and propylene are used to produce propylene oxide at a
rate of 100 metric tons per day, with methanol serving as the solvent.
Calculation of the material and energy balances as well as their thorough diagrammatic
representations are also offered. Each individual processing equipment, such as the reactor,
heat exchanger, stripper, flash separator, and distillation column, has undergone mass and
energy balance studies. Reactor, heat exchanger, flash separator and its mechanical design,
distillation column and detailed design calculations are also displayed with instrumentation
and control. Environmental impact assessment and HAZOP have also been included. The
EIA is followed by a cost estimate for the complete plant. Additionally, this comprehensive
report is a source of data on propylene oxide production, which encourages its production
in Pakistan and helps turn Pakistan into a good exporter.
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ACKNOWLEDGMENTS
All praise to ALLAH ALMIGHTY, the most merciful WHO enabled us to accomplish
this Project.
All respects are for The HOLY PROPHET (Peace Be Upon Him), whose teachings are
true source of knowledge & guidance for whole mankind.
We are greatly thankful to our Parents whose prayers led to our success, they stood by us
and through thick and thin and supported us throughout our lifetime.
We acknowledge our indebtedness to our advisor, Engr. Mehboob Ahmad Aadil for his
timely guidance, encouragement, sympathetic attitude and professional assistance without
whom this project would not have been completed.
We would like to mention the Head of Chemical Engineering Department, Dr. Asim Umer
for his guidance.
We are also thankful to our teachers Dr. Ayyaz Ahmed, Dr. Athar and Dr. Mehran for their
keen and sincere efforts and suggestions during our project calculations and thesis
preparation that proved to be very helpful in achieving our goal.
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TABLE OF CONTENTS
CHAPTER 1: INTRODUCTION .....................................................................................1
1.1. Introduction ............................................................................................................. 1
1.2. Propylene Oxide ...................................................................................................... 1
1.3. Uses of Propylene Oxide ......................................................................................... 2
1.4. Chemical Properties ................................................................................................ 2
1.5. Physical Properties .................................................................................................. 4
1.6. Thermodynamic Properties ..................................................................................... 4
1.7. Propylene (Reactant) ............................................................................................... 4
1.8. Availability of Propylene ........................................................................................ 5
1.9. Hydrogen Peroxide (Oxidizing Reactant) ............................................................... 5
1.10. Properties of Hydrogen Peroxide .......................................................................... 6
1.11. Availability of Hydrogen Peroxide ....................................................................... 6
1.12. Methanol (Solvent) ................................................................................................ 7
Properties of Methanol................................................................................... 7
1.13. Propylene Glycol (Side Product) ........................................................................... 7
1.14. Titanium-Silicalite TS-1 (Catalyst) ....................................................................... 7
Application (Catalyst) .................................................................................... 8
1.15. Market Analysis .................................................................................................... 8
Imports ........................................................................................................... 8
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Top Importers of Methyloxirane (Propylene Oxide) in 2020 ........................ 8
Exports ........................................................................................................... 9
Top Exporters of Methyloxirane (Propylene Oxide) in 2020 ........................ 9
Worldwide Major Propylene Oxide Production Companies ....................... 10
1.16. Market of Propylene Oxide in China .................................................................. 11
China Imports of Propylene Oxide .............................................................. 11
China Import of Propylene Oxide in USD/Year .......................................... 11
China Import of Propylene Oxide in Tons/Year .......................................... 12
1.17. Capacity Selection ............................................................................................... 12
References .................................................................................................................... 12
CHAPTER 2: LITERATURE REVIEW ......................................................................14
2.1. Chlorohydrin Process ............................................................................................ 14
Process ........................................................................................................... 14
2.2. The Indirect Oxidation Processes .......................................................................... 15
Oxidation of Isobutane to T-butyl Hydroperoxide and T-butyl Alcohol ...... 15
Ethylbenzene Hydroperoxide Process ........................................................... 17
Other Indirect Oxidation Processes ............................................................... 18
2.3. Direct Oxidation Processes ................................................................................... 18
2.4. Hydrogen Peroxide Process (HPPO) ..................................................................... 19
2.5. Patented Silver-Based Catalyst Process ................................................................ 20
2.6. Process Selection ................................................................................................... 22
2.7. Rate Laws .............................................................................................................. 22
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2.8. Effects of Parameters and Their Selection ............................................................ 22
Effect of Methanol (Solvent) ......................................................................... 22
Effect of Pressure ........................................................................................... 23
Effect of Temperature .................................................................................... 23
Process Flow Diagram ................................................................................... 24
2.9. Process Description ............................................................................................... 25
Process Overview .......................................................................................... 25
2.10. Detailed Process Description............................................................................... 26
Feed Preparation .......................................................................................... 26
Reactor ......................................................................................................... 27
Pre-Separation Section ................................................................................. 27
Propylene Oxide Distillation Column.......................................................... 28
Methanol-Water Distillation Column .......................................................... 28
References .................................................................................................................... 28
CHAPTER 3: LAW OF CONSERVATIONS...............................................................30
3.1. Conservation of Mass ............................................................................................ 30
Introduction .................................................................................................... 30
Basis for Calculations .................................................................................... 30
Material Balance Across Reactor .................................................................. 30
Material Balance Across Flash Column ........................................................ 31
Mass Balance Across Stripper ....................................................................... 34
Material Balance Across Distillation Column 1 ............................................ 35
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Material Balance Across Distillation Column 2 ............................................ 36
Overall Balance.............................................................................................. 38
3.2. Conservation of Energy ......................................................................................... 39
Introduction .................................................................................................... 39
Energy Balance Across Heat Exchangers ...................................................... 39
Energy Balance Across Mixer ....................................................................... 41
Energy Balance Across Reactor .................................................................... 41
Energy Balance Across Flash Column .......................................................... 43
Energy Balance Across Stripper .................................................................... 45
Energy Balance Across Distillation Columns ............................................... 46
References .................................................................................................................... 47
CHAPTER 4: EQUIPMENT DESIGN .........................................................................49
4.1. Reactor Design ...................................................................................................... 51
Selection Criteria ........................................................................................... 51
Design Steps .................................................................................................. 55
Reaction Mechanism...................................................................................... 56
Kinetics .......................................................................................................... 56
Rate Constant ................................................................................................. 56
Performance Equation.................................................................................... 56
Graph ............................................................................................................. 57
Weight of Catalyst ......................................................................................... 57
Volume of Catalyst Bed ................................................................................. 58
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Volume of Reactor ....................................................................................... 58
Residence Time............................................................................................ 58
Number of Tubes Required.......................................................................... 58
Tube Dimensions ......................................................................................... 59
Tube Side Heat Transfer Coefficient ........................................................... 59
Shell Side Heat Transfer Coefficient ........................................................... 60
Overall Heat Transfer Coefficient ............................................................... 61
Area Required .............................................................................................. 61
Pressure Drop on Tube Side ........................................................................ 62
Pressure Drop on Shell Side ........................................................................ 62
Specification Sheet of Reactor ..................................................................... 63
4.2. Flash Separator Design .......................................................................................... 63
Gas-Liquid Separators: .................................................................................. 63
Types of Flash Separators .............................................................................. 63
Selection Criteria ........................................................................................... 64
Internals of Flash Separator ........................................................................... 64
Design Steps: ................................................................................................. 65
Preliminary Information ................................................................................ 66
Designing Calculations .................................................................................. 66
4.3. Mechanical Design ................................................................................................ 68
Calculations for Cylindrical Shell: ................................................................ 68
Specification Sheet for Flash Column: .......................................................... 69
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4.4. Distillation Column Design ................................................................................... 70
Reason for using Distillation Column ........................................................... 70
Types of Distillation ...................................................................................... 70
Choice Between Tray and Packed Column ................................................... 72
Design Steps .................................................................................................. 73
Design Conditions: ........................................................................................ 74
Minimum Number of stages .......................................................................... 74
Reflux Ratio ................................................................................................... 74
Theoretical Number of Stages ....................................................................... 75
Vapor & Liquid Flowrate .............................................................................. 75
Diameter of Distillation Column ................................................................. 76
Overall Tray Efficiency ............................................................................... 77
Liquid Flow Arrangements .......................................................................... 77
Height of Distillation Column ..................................................................... 77
Weir Dimensions: ........................................................................................ 78
Weeping ....................................................................................................... 78
Actual Minimum Vapor Velocity ................................................................ 79
Pressure Drop ............................................................................................... 79
Down-Comer Liquid Backup....................................................................... 80
Residence Time............................................................................................ 80
Entrainment.................................................................................................. 80
Perforated Area ............................................................................................ 81
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Number of Holes .......................................................................................... 81
Length/Diameter (L/D) Ratio ...................................................................... 81
Specification Sheet of Distillation Column ................................................. 82
4.5. Heat Exchanger Design ......................................................................................... 82
Design of Key Exchanger Type ..................................................................... 83
Types of Heat Exchanger ............................................................................... 83
Preliminary Selection:.................................................................................... 84
Fluid Placement ............................................................................................. 85
Design Steps .................................................................................................. 86
Pressure Drop calculation .............................................................................. 89
4.6. Simulation of Plant ................................................................................................ 91
Procedure: ...................................................................................................... 92
Calculations ................................................................................................... 95
References .................................................................................................................. 101
CHAPTER 5: ENVIRONMENTAL SAFETY AND CONTROL STUDY ..............104
5.1. Instrumentation and Control................................................................................ 104
Instrumentation ............................................................................................ 104
Control ......................................................................................................... 104
Instrumentation and Control Objectives ...................................................... 105
Variables in a Chemical Process .................................................................. 105
Design Elements of a Control System ......................................................... 106
Components of the Control System ............................................................. 106
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Types of Control Configuration ................................................................... 106
Types of Controller ...................................................................................... 107
5.2. Distillation Column Control System ................................................................... 107
Distillation Control Objectives .................................................................... 107
Control on Distillation Column ................................................................... 108
Piping and Instrumentation Diagram of Distillation Column...................... 109
5.3. HAZOP Study ..................................................................................................... 110
Purpose of HAZOP Study............................................................................ 110
Advantages of HAZOP ................................................................................ 110
HAZOP Flowchart ....................................................................................... 111
5.4. HAZOP Study of Heat Exchanger ...................................................................... 111
5.5. EIA Study ............................................................................................................ 111
Introduction to Environmental Impact Assessment ..................................... 111
Importance of EIA ....................................................................................... 112
Contents of EIA ........................................................................................... 112
Proposed Plant Location .............................................................................. 112
Physical Baseline ......................................................................................... 112
Environment Impact During the Construction of Plant ............................... 114
Environmental Impacts and Mitigation Associated with Operational
Activities: ....................................................................................................... 116
EIA of Propylene Oxide .............................................................................. 116
References .................................................................................................................. 119
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CHAPTER 6: ECONOMICS OF PLANT ..................................................................121
6.1. Introduction ......................................................................................................... 121
The Engineer’s Role in Profit Creation ....................................................... 121
Capital Requirements ................................................................................... 122
Cost Escalation ............................................................................................ 122
Cash Flow .................................................................................................... 123
Rate of Return (ROR) .................................................................................. 123
Pay-Back Time ............................................................................................ 123
Turnover Ratio ............................................................................................. 124
Manufacturing Costs .................................................................................... 124
6.2. Estimating Purchased Equipment Costs .............................................................. 124
Cost Estimation of Reactor .......................................................................... 125
Cost Estimation of Distillation Column....................................................... 125
Cost Estimation of Stripper.......................................................................... 126
Cost Estimation of Flash Column ................................................................ 126
Cost Estimation of Pump ............................................................................. 127
Cost Estimation of Mixer............................................................................. 127
Total Equipment Cost .................................................................................. 128
6.3. Fixed Capital Investment..................................................................................... 128
6.4. Direct Cost ........................................................................................................... 128
6.5. Indirect Cost ........................................................................................................ 129
6.6. Working Capital Investment ............................................................................... 129
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6.7. Total Capital Investment ..................................................................................... 129
6.8. Total Product Cost ............................................................................................... 129
6.9. Raw Material Cost ............................................................................................... 130
6.10. General Expenses .............................................................................................. 130
6.11. Gross Earning/Income ....................................................................................... 130
6.12. Net Profit ........................................................................................................... 131
6.13. Rate of Return ................................................................................................... 131
6.14. Payback Period .................................................................................................. 131
References .................................................................................................................. 131
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LIST OF FIGURES
Figure Page
Figure 1-1 Propylene Oxide Structure ................................................................................ 2
Figure 1-2 Worldwide Imports of Propylene Oxide (2020) ............................................... 9
Figure 1-3 Worldwide Exports of Propylene Oxide (2020) ............................................. 10
Figure 1-4 Worldwide Major Propylene Oxide Producer................................................. 10
Figure 1-5 China Import of Propylene Oxide in USD/Year ............................................. 11
Figure 1-6 China Import of Propylene Oxide in Tons/Year ............................................. 12
Figure 2-1 Effect of Temperature on Selectivity .............................................................. 23
Figure 3-1 Reactor (R-101) Mass Balance ....................................................................... 31
Figure 3-2 Flash Column (FC-101) Mass Balance ........................................................... 34
Figure 3-3 Stripper (ST-101) Mass Balance ..................................................................... 35
Figure 3-4 Distillation Column (DC-101) Mass Balance ................................................. 36
Figure 3-5 Distillation Column (DC-101) Mass Balance ................................................. 37
Figure 3-6 Overall Balance ............................................................................................... 38
Figure 3-7 Energy Balance Across Heat Exchanger 1 ...................................................... 40
Figure 3-10 Mixer Energy Balance................................................................................... 41
Figure 3-11 Reactor (R-101) Energy Balance .................................................................. 42
Figure 3-12 Flash Column (FC-101) Energy Balance ...................................................... 44
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Figure 3-13 Stripper (ST-101) Energy Balance ................................................................ 45
Figure 3-14 Distillation Column (DC-101) Energy Balance ............................................ 46
Figure 3-15 Distillation Column (DC-102) Energy Balance ............................................ 47
Figure 4-1 Different Types of Fixed/Packed Bed Reactor ............................................... 55
Figure 4-2 Conversion Vs 1/-r Graph ............................................................................... 57
Figure 4-3 Log Mean Temperature Difference ................................................................. 61
Figure 4-4 Flash Column Internals ................................................................................... 64
Figure 4-5 System Constant .............................................................................................. 66
Figure 4-6 Structure for the Process of Heat Exchanger Design Logic ............................ 83
Figure 4-7 LMTD for Heat Exchanger ............................................................................. 87
Figure 4-8 Adding of Components in Aspen HYSYS ...................................................... 92
Figure 4-9 Adding Fluid Package in Aspen HYSYS ....................................................... 92
Figure 4-10 Adding Reaction Set in Aspen HYSYS ........................................................ 93
Figure 4-11 Adding Reactions in Aspen HYSYS............................................................. 93
Figure 4-12 Adding Coefficients of Reaction 1 ................................................................ 94
Figure 4-13 Adding Coefficients of Reaction 2 ................................................................ 94
Figure 4-14 Worksheet of Pump (P-101).......................................................................... 95
Figure 4-17 Worksheet of Heat Exchanger (HX-101) ...................................................... 96
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Figure 4-20 Worksheet of Mixer (MIX-101).................................................................... 98
Figure 4-21 Worksheet of Reactor (R-101) ...................................................................... 98
Figure 4-22 Worksheet of Valve (VLV-101) ................................................................... 99
Figure 4-23 Worksheet of Flash Column (FC-101).......................................................... 99
Figure 4-24 Worksheet of Stripper (St-101) ................................................................... 100
Figure 4-25 Worksheet of Distillation Column (DC-101).............................................. 100
Figure 4-26 Worksheet of Distillation Column (DC-102).............................................. 101
Figure 5-1 Distillation Column P&ID Diagram ............................................................. 109
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LIST OF TABLES
Table 1-1 Thermodynamic Properties of Propylene Oxide ................................................ 4
Table 1-2 Properties of Propylene ...................................................................................... 5
Table 1-3 Properties of Hydrogen Peroxide ....................................................................... 6
Table 1-4 Properties of Methanol ....................................................................................... 7
Table 2-1 Other Indirect Oxidation Processes .................................................................. 18
Table 2-2 Comparison of Propylene Manufacturing Processes ........................................ 21
Table 3-1 Antoine Constants ............................................................................................ 32
Table 3-2 Bubble Pressure calculation ............................................................................. 32
Table 3-3 Dew Pressure calculation ................................................................................. 33
Table 3-4 Flash Pressure Calculations .............................................................................. 33
Table 3-5 Overall Balance ................................................................................................ 38
Table 3-6 Heat Capacity Coefficients ............................................................................... 39
Table 3-7 Heat of Formation Coefficients ........................................................................ 42
Table 3-8 Heat of Vaporization Coefficients .................................................................... 43
Table 4-1 Continuous Vs Batch Reactor .......................................................................... 52
Table 4-2 Comparison of CSTR and PFR ........................................................................ 52
Table 4-3 Comparison of Fixed Bed Reactor and Fluidized Bed Reactor ....................... 53
Table 4-4 Tube Selection .................................................................................................. 59
Table 4-5 Types of Separators .......................................................................................... 64
Table 4-6 Head Selection .................................................................................................. 69
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Table 4-7 Trays vs Packing............................................................................................... 72
Table 4-8 Types of Trays .................................................................................................. 73
Table 4-9 Feed Conditions of Distillation Column........................................................... 74
Table 4-10 Heat Exchanger Types with Their Features and Limitations ......................... 84
Table 4-11 Selection Between Double Pipe and Shell & tube Heat Exchanger ............... 85
Table 4-12 Dimensions for Double Pipe Heat Exchanger ................................................ 88
Table 5-1 Temperature Control of Distillation Column ................................................. 108
Table 5-2 Level Control of Distillation Column............................................................. 108
Table 5-3 Composition Control of Distillation Column ................................................. 109
Table 5-4 HAZOP Study of Heat Exchanger ................................................................. 111
Table 6-1 All Equipment Capital Cost............................................................................ 128
Table 6-2 Direct Cost ...................................................................................................... 128
Table 6-3 Indirect Cost ................................................................................................... 129
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List of Abbreviations
Symbol Description
Atm Atmospheric Pressure
Cp Heat Capacity
CSTR Continuous Stirring Tank Reactor
EO Ethylene Oxide
HPPO Hydrogen Peroxide to Propylene Oxide
kJ Kilojoule
kW Kilowatt
MRs. Million Rupees
MTPD Metric Ton Per Day
M.W Molecular Weight
PFR Plug Flow Reactor
PO Propylene Oxide
Q Heat
TS-1 Titanium Silicalite 1
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CHAPTER 1: INTRODUCTION
1.1. Introduction
Epoxy Propane (Propylene Oxide) is an important chemical intermediate [1]. It serves as a building
block for a variety of products such as polyether polyols, propylene glycols and propylene glycol
ethers. Polyether polyol (polymeric polyol) is mainly used to make polyurethane foams, which is
the main raw material used in the production of flexible foams for car seats, home furniture and
rigid foams used for insulation in buildings and construction. Propylene glycol is used to make
unsaturated polyester resins, cosmetics, antifreezes, and pharmaceuticals, while propylene glycol
ethers are used in the production of paints, solvents, and coatings [2].
Propylene oxide is currently produced by two different commercial processes, i.e. the chlorohydrin
process and the hydroperoxidation process. However, both of these processes suffer from
inevitable drawbacks. The former is not environmentally friendly due to the use of
environmentally hazardous chlorine and the production of chlorinated organic by-products as well
as calcium chloride. The second method produces equimolar amounts of by-products, styrene or
tert-butanol, and the viability of this process depends on the existence of a market for such by-
products [3].
Several companies are developing innovative technologies to produce PO that are efficient, cost-
effective and environmentally friendly. Over the years, the global demand for PO has steadily
increased, and therefore it is produced as a high-volume industrial chemical.
1.2. Propylene Oxide
Propylene oxide (methyloxirane, 1,2-epoxypropane) is an important organic chemical used

primarily as a reaction intermediate for the production of polyether polyols, propylene glycol,
alkanolamines, glycol ethers and many other useful products (e.g. glycols) [1]. Propene oxide (PO)
is one of the largest propylene derivatives in production, second only to polypropylene [4].
Propylene oxide was first prepared in 1861 by Oser and first polymerized by Levene and Walti in
1927 [5]. Although not as reactive as ethylene oxide (EO), propylene oxide is also the basis of a
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versatile and rapidly expanding chemistry [6]. Since the beginning of the 1950s, it has been gaining
importance for the chemical industry and demand for PO continues to grow worldwide. [2]
The chemical structure of PO differs from EO by the methyl group (–CH 3). The difference is more
than a matter of geometric symmetry. For example, the methyl group in PO adversely increases
the reactivity of the molecule. [7]
Figure 1-1 Propylene Oxide Structure
1.3. Uses of Propylene Oxide
 Propylene oxide (PO) is used in the production of polyurethane polyols (60-65%),

propylene glycols (20-25%), P series glycol ethers (3-5%), di- and tripropylene glycols (3-
5%) and other various chemicals (10%), which include polyalkylene glycols, allyl alcohol
and isopropylamines [1], [8].
 Polyurethane polyols are used in the production of polyurethane foams, while propylene
glycols are used to produce unsaturated polyester resins for the textile and construction
industries [9].
 Propylene glycols are also used in pharmaceuticals, cosmetics, solvents and emollients in
foods, plasticizers, heat transfer and hydraulic fluids, and antifreezes.
 PO also finds use in the sterilization of packaged foods and as a pesticide [10].
1.4. Chemical Properties
 PO is a highly reactive, versatile chemical intermediate. Its polarity and strained three-
membered epoxy ring make it readily open by reaction with a wide variety of substances.
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In this respect it is analogous to ethylene oxide and the number of possible derivatives is
very large. [2]
 Most industrial reactions are catalyzed by PO, although PO itself readily reacts with all
compounds containing active hydrogen atoms (including hydrogen halides), as well as
chlorine and ammonia. Alkaline catalysts (e.g. sodium hydroxide, sodium acetate, sodium
alkoxide or potassium alkoxide) are preferred. Acidic materials such as sulfuric acid, boron
fluoride, stannous chloride, or acid clays (which are sometimes used at lower reaction
temperatures) often form byproducts by converting oxides to cyclic ethers or isomerizing
them to aldehydes.
 The most important type of reaction is the addition of PO to compounds containing labile
hydrogen, but it also condenses with a number of substances that do not contain reactive
hydrogen.
 The most important reaction of PO from a commercial point of view is its rapid
polymerization to form poly (ether polyols) in the presence of catalysts such as bases, acids
or salts. Chain initiators are substances containing active hydrogen atoms (eg water,
glycols, phenols, amines or carboxylic acids). PO forms mixed polyols with ethylene oxide,
tetrahydrofuran, 3,4-epoxy-1-butene (butadiene monoxide) and carbon dioxide.
 PO is hydrolyzed by water in an uncatalyzed reaction in the liquid phase to form
monopropylene glycol, dipropylene glycol, tripropylene glycol and polyglycols. PO reacts
with ketones or aldehydes to form cyclic ketals or acetals and with carbon dioxide to form
propylene carbonate. Hydrogen halides convert PO into propylene halohydrins, and
ammonia yields mono-, di-, and tri-isopropanolamine.
 Via aluminum oxide, PO isomerizes to propanal and acetone, and via Li 3PO4 catalysts to
allyl alcohol. Hydrogenation on nickel leads to 1-propanol. Many other reactions are also
possible, including reactions with natural products such as starch or cellulose.
 All reactions involving PO can become violent if not properly controlled, and possible
applications should be very thoroughly investigated. Under pyrolytic conditions, PO
isomerizes to propanal, acetone, methyl vinyl ether and allyl alcohol [11]. The
decomposition of PO does not result in the formation of dangerous products.
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 PO is a stable compound under mild conditions, but polymerization can occur on contact
with highly active catalytic surfaces such as iron, tin, or aluminum chlorides, iron-
aluminum peroxides or alkali metal hydroxides, and clay-based absorbent materials.
Anything that disrupts the neutrality of PO can also cause polymerization.
1.5. Physical Properties

 Propylene oxide, C3H6O, M.W (58.081), is a colorless, low-boiling liquid with a sweet,
ethereal odor. [2]
 It is also reactive and highly flammable, with a wide explosive range.
 Flammable vapor concentrations are easily formed at room temperature.
1.6. Thermodynamic Properties

Table 1-1 Thermodynamic Properties of Propylene Oxide
Properties Value
Molecular weight 58.08
Boiling Point at 101.325 kPa 34.2 °C
Freezing Point -111.93 °C
Critical Pressure 4.92 MPa
Critical Temperature 209.1 °C
3
Critical Volume 186 cm /mol
Flash Point -37 °C
Heat of Fusion 6.531 kJ/mol
Heat of vaporization 27.8947 kJ/mol
Heat of Combustion 1915.6 kJ/mol
Specific Heat at 20 °C 122.19 kJ/mol
Autoignition Temperature 465 °C
1.7. Propylene (Reactant)
 Propylene is perhaps the oldest petrochemical feedstock and is one of the principal light
olefins. [1]
 It is used widely as an alkylation or polymer-gasoline feedstock for octane
improvement
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 Contact with the liquid can cause frostbite.

 The vapors are heavier than air.
 It can asphyxiate by the displacement of air
1.8. Availability of Propylene
 There are a number of industries that are producing polypropylene in Pakistan [12] by using
propylene as a raw material and imports of propylene in Pakistan is negligible [13]. So,
propylene is available in Pakistan.
 Furthermore, propylene can also be imported from Azerbaijan at low cost because
Azerbaijan is exporting a large amount or propylene every year. [13]
Properties of Propylene
Table 1-2 Properties of Propylene
Formula CH3CH=CH2
Molar mass 42.081
Appearance Colorless gas
Density 0.5139 g/cm³ (at 20 °C)
Melting Point -185°C (-301°F)
Boiling point -43.8 °F (-42.11 °C)
Flash point -156 °F (-104.44 °C)
Viscosity 8.34 µPa·s at 16.7 °C
Solubility in water Poor
Auto-ignition temp. 455 °C (851°F)
Critical temperature 365.57 K
1.9. Hydrogen Peroxide (Oxidizing Reactant)
 Hydrogen peroxide is a strong oxidizing agent commercially available in aqueous solution

over a wide range of concentrations. [14]
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 It is a weakly acidic, nearly colorless dear liquid that is miscible with water in all
proportions.
 The atoms are covalently bound in a nonpolar structure having association (hydrogen
bonding) somewhat less than that found in water.
1.10. Properties of Hydrogen Peroxide
Table 1-3 Properties of Hydrogen Peroxide
Chemical formula H2O2

Molar mass 34.0147 g/mol
Appearance Very light blue color; colorless in solution
Odor slightly sharp
Density 1.450 g/cm3 (20 °C, pure)
Melting point −0.43 °C (31.23 °F; 272.72 K)
Boiling Point 150.2 °C (302.4 °F; 423.3 K) (decomposes)
Solubility in water Miscible
Solubility Soluble in ether, alcohol
Insoluble in petroleum ether
Vapor pressure 5 mmHg (30 °C)
Viscosity 1.245 cP (20 °C)
Heat capacity 1.267 J/(g·K) (gas)
2.619 J/(g·K) (liquid)
1.11. Availability of Hydrogen Peroxide
 The domestic industry currently comprises two players:
i) Descon Oxychem Limited – Installed annual capacity 35400 MT [15]
ii) Sitara Peroxide Limited – Installed annual capacity 30,000 MT [16]
 Both the companies are also looking forward to increase their capacity
 Engro Polymer & Chemicals is also planning to enter the market in with a capacity of
20,000 MT. [17]
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1.12. Methanol (Solvent)
 Methanol is a colorless liquid at ambient temperatures with a mild, characteristic alcohol

odor. [18]
 Originally called wood alcohol since it was obtained from the destructive distillation of
wood, today commercial methanol is sometimes referred to as synthetic methanol because
it is produced from synthesis gas, a mixture of hydrogen and carbon oxides, generated by
a variety of sources.
Properties of Methanol
Table 1-4 Properties of Methanol
Chemical formula CH3OH or CH4O

Molar mass 32.04 g mol−1
Appearance Colorless liquid
Odor Sweet and pungent
Density 0.792 g/cm3
Melting point −97.6 °C (−143.7 °F; 175.6 K)
Boiling Point 64.7 °C (148.5 °F; 337.8 K)
Solubility in water Miscible
Vapor pressure 0.545 mPa·s (at 25 °C)
1.13. Propylene Glycol (Side Product)
 The propylene glycol family of chemical compounds consist of monopropylene glycol,

dipropylene glycol and tripropylene glycol. [19]
 Propylene Glycols are clear, viscous colorless liquids that have very little odor a
slightly bittersweet taste, and low vapor pressures.
 They are available as highly purified product.
1.14. Titanium-Silicalite TS-1 (Catalyst)
 Medium pore TS-1 is a highly versatile zeolite that is used as an effective catalyst in a
variety of industrial applications. [20]
7|Page
 TS-1 demonstrates unique catalytic performance in oxidation reactions involving H 2O2 as

an oxidant.
 Catalyst TS-1 is highly effective in the selective oxidation of various organic substrates
with hydrogen peroxide, including hydroxylation of aromatics, epoxidation of alkenes,
ammoximation of ketones, oxidation of alkanes and alcohols, etc.
Application (Catalyst)
 Titanium-Silicalite TS-1 has attracted attention due to its excellent catalytic properties
in partial oxidation of many organic compounds‚ including: [21]
 Alkene epoxidation
 Cyclohexanone ammoxidation
 Alcohol oxidation
 Oxidation of saturated hydrocarbon
 Hydroxylation of aromatic hydrocarbon
1.15. Market Analysis
World production of propylene oxide exceeds 2000 kilotons per year, most of which is used as a
chemical intermediate. [22]
Imports
In 2020, the world imports of "Methyloxirane (propylene oxide)" exceeded $1.84 billion
(according to external trade statistics of 61 countries). It was $2.19 billion in the previous year
(according to merchandise trade statistics of 60 countries). [23]
Top Importers of Methyloxirane (Propylene Oxide) in 2020
Following are the top importers of Propylene Oxide: [23]
 China - 31% of the world imports ($573 million)

 Netherlands - 15.1% ($279 million)  Belgium - 14.8% ($272 million)
 Germany - 12.8% ($236 million)  Asia - 5.85% ($107 million)
8|Page
Figure 1-2 Worldwide Imports of Propylene Oxide (2020)
Exports
In 2020, the world exports of "Methyloxirane (propylene oxide)" exceeded $1.72 billion
(according to external trade statistics of 30 countries). It was $2 billion in the previous year
(according to merchandise trade statistics of 25 countries). [23]
Top Exporters of Methyloxirane (Propylene Oxide) in 2020
Following are the top exporters of Propylene Oxide: [23]
 Netherlands - 27% of the world exports ($479 million)

 USA - 14.3% ($247 million)
 Saudi Arabia - 10.7% ($185 million)
 Germany - 10.7% ($184 million)
 Korea - 9.96% ($171 million)
 Belgium - 7.34% ($126 million)
9|Page
Figure 1-3 Worldwide Exports of Propylene Oxide (2020)
Worldwide Major Propylene Oxide Production Companies

The propylene oxide market is a fragmented market, where numerous players hold an insignificant
share to affect the market dynamics individually. Some of the noticeable players in the market
include: [24]
Figure 1-4 Worldwide Major Propylene Oxide Producer
10 | P a g e
1.16. Market of Propylene Oxide in China
The value of imports of commodity group "Methyloxirane (propylene oxide)" to China totaled $
573 million in 2020. Sales of commodity group to China went up by 4.78% compared to 2019:
imports of commodity group "Methyloxirane (propylene oxide)" went up by $ 26 million (the
value of imports of commodity group to China was equal to $547 million in 2019) [23]
On average (2015-2018) China requires 736 MTPD of Propylene Oxide
China Imports of Propylene Oxide
Top trading partners (import of "Methyloxirane (propylene oxide)") of China in 2020: [23]
 Saudi Arabia  Korea  USA
 Thailand  Japan  Singapore
 Netherland  Spain  Germany
 Belgium
China Import of Propylene Oxide in USD/Year
600 573.241
547.041
AMOUNT (USD) (MILLION)
450 393.955
321.948
300 266.74
150
0
2016 2017 2018 2019 2020
YEAR
Figure 1-5 China Import of Propylene Oxide in USD/Year
11 | P a g e
China Import of Propylene Oxide in Tons/Year
300000 299596 281882

261142
232547
AMOUNT (TONS)
200000
100000
0
2015 2016 2017 2018
YEAR
Figure 1-6 China Import of Propylene Oxide in Tons/Year
1.17. Capacity Selection
China is one of the largest importers of Epoxy Propane (Propylene Oxide) and importing highest
amount of it. Pakistan has good relations with China. So, it can be targeted as a potential long-term
customer with the CPEC agreement already in place. Moreover, by setting up an Epoxy Propane
(Propylene Oxide) plant in Pakistan, job opportunities will arise and the trade deficit of Pakistan
will decrease by increasing the export of Epoxy Propane. So, by considering the availability of
raw materials, the selected capacity of plant is 100 MTPD.
References
[1] J. Logsdon, "Kirk-Othmer Encyclopedia of Chemical Technology: Power Generation to

Recycling," vol. 20, ed: John Wiley & Sons 2001.
[2] B. Elvers, Ullmann's encyclopedia of industrial chemistry. Verlag Chemie Hoboken, NJ,
1991.
[3] L. Wang et al., "Epoxidation of Propylene Over Titanosilicate-1 in Fixed-bed Reactor:
Experiments and Kinetics," Asian Journal of Chemistry, vol. 26, no. 4, 2014.
[4] F. Cavani, G. Centi, S. Perathoner, and F. Trifirò, Sustainable industrial chemistry:
Principles, tools and industrial examples. John Wiley & Sons, 2009.
12 | P a g e
[5] J. H. Saunders and K. C. Frisch, Polyurethanes: chemistry and technology. Interscience

Publishers, 1962.
[6] K. Weissermel and H.-J. Arpe, Industrial organic chemistry. John Wiley & Sons, 2008.
[7] D. L. Burdick and W. L. Leffler, "Petrochemicals in nontechnical language," 1990.
[8] chemexpo.com, Chemical Profile. Chemexpo.com, 9/10/2001.
[9] S. T. Oyama, "Rates, kinetics, and mechanisms of epoxidation: homogeneous,
heterogeneous, and biological routes," in Mechanisms in homogeneous and heterogeneous
epoxidation catalysis: Elsevier, 2008, pp. 3-99.
[10] "Hazardous Substance Data Bank, Online database produced by the National Library of
Medicine, 1,2-Propylene Oxide Profile last updated, (October 10, 2001).".
[11] M. C. Flowers, "Kinetics of the thermal gas-phase decomposition of 1, 2-epoxypropane,"
Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in
Condensed Phases, vol. 73, pp. 1927-1935, 1977.
[12] businessbook.pk/category/polypropylene-2646.
[13] data.un.org Commodity Trade Statistics Database. UN DATA.
[14] J. Logsdon, Kirk-Othmer Encyclopedia of Chemical Technology: Helium Group to
Hypnotics, Sedatives, Anticonvulsants and Anxiolytics John Wiley & Sons, 2001.
[15] descon.com. Descon Oxychem Limited, 2022.
[16] sitaraperoxide.com. Sitara Peroxide Limited, 2022.
[17] profit.pakistantoday.com.pk. Profit Pakistantoday, 2018.
[18] J. Logsdon, Kirk-Othmer Encyclopedia of Chemical Technology: Matches to
Neuroregulators John Wiley & Sons, 2001.
[19] J. Logsdon, Kirk-Othmer Encyclopedia of Chemical Technology: Fuel resources to heat
stabilizers John Wiley & Sons, 2001.
[20] R. Millini, E. P. Massara, G. Perego, and G. Bellussi, "Framework composition of titanium
silicalite-1," Journal of Catalysis, vol. 137, no. 2, pp. 497-503, 1992.
[21] A. Thangaraj, M. Eapen, S. Sivasanker, and P. Ratnasamy, "Studies on the synthesis of
titanium silicalite, TS-1," Zeolites, vol. 12, no. 8, pp. 943-950, 1992.
[22] wedocs.unep.org. World Health Organization.
[23] trendeconomy.com/data/commodity_h2/291020. World Merchandise Exports and Imports
by Commodity.
[24] mordorintelligence.com/industry-reports/propylene-oxide-market. Mordor Intelligence.
13 | P a g e
CHAPTER 2: LITERATURE REVIEW
2.1. Chlorohydrin Process
The chlorohydrin route takes two steps. Reaction of propylene with hypochlorous acid (HO–Cl)
followed by dehydrochlorination of the propylene chlorohydrin with calcium hydroxide. Three
equations describe the process. The first involves making the hypochlorous acid by reacting
chlorine and water. In the second, the acid reacts with propylene to make chlorohydrin. The
dehydrochlorination takes place in the third to give propylene oxide. [1]
 Hypochlorous Acid
Cl + H O → HOCl + HCl
 Formation of Propylene Chlorohydrin
C H + HOCl → C H ClO
 Dehydrochlorination
C H ClO + Ca(OH) → 2C H O + CaCl + 2H O

Process
Two of the reactions take place in the same reactor in this plant. The formation of the hypochlorous
acid (HOCl) from chlorine and water, and the reaction with propylene all occur simultaneously.
Propylene reacts readily with chlorine to form that unwanted by-product, propylene dichloride. To
limit that, the HOCl and HCl are kept very dilute. But as a consequence, the concentration of the
propylene chlorohydrin leaving the reactor is very low, only 3%–5%. At any higher concentration,
a separate phase or second layer in the reactor would form. It would preferentially suck up
(dissolve) the propylene and chlorine coming in, leading to runaway dichloride yields. The low
concentration levels of the propylene chlorohydrin and the need to recycle so many pounds of
material are the reasons the process is so energy intensive. It just takes a lot of electricity to pump
all that stuff around. [1]
The unreacted propylene is taken off the top of the reactor and cleaned up for recycling. By
bubbling this stream through a dilute caustic solution (like sodium hydroxide, NaOH), the chlorine
and HCl carried along with the propylene are removed by converting them to sodium chloride,
14 | P a g e
NaCl, and water. The “scrubbed” propylene is then taken overhead (from the top of the
fractionation column) and is ready as fresh feed or use elsewhere in the plant. [1]
The dilute propylene chlorohydrin stream is mixed with a solution of water and 10% slaked lime
[calcium hydroxide, Ca(OH)2] and pumped to a vessel called the hydrolyzer. The chlorohydrin
rapidly dehydrates to PO. The reaction is so fast that the PO has to be sprung from the mixture
before the reaction continues and goes to propylene glycol. Steam is bubbled through the reactor,
helping to flash (vaporize) the PO out of the reaction zone. [1]
The vapor from the hydrolyzer contains not only water and PO but also propylene dichloride and
whatever other products (by-products) get created. Fractionation columns are used to purify the
PO to a 99% technical grade. [1]
2.2. The Indirect Oxidation Processes
The indirect oxidation route also takes two steps. In the first, a hydrocarbon, such as isobutane,
ethylbenzene, or cumene, is oxidized. The source of the oxygen is air. The reaction takes place
just by mixing the ingredients and heating them to produce hydroperoxide. In the second step, the
oxidized hydrocarbon reacts with propylene to produce PO yields of better than 90%. [1]
Oxidation of Isobutane to T-butyl Hydroperoxide and T-butyl Alcohol
The two main stages can be distinguished as: [2]

 Production of hydroperoxide
 Epoxidation of propylene
Production of Hydroperoxide
The reaction takes place by oxygen in the liquid phase in several series of agitated reactors, each
series laid out in parallel in the same horizontal shell. The reaction takes place without catalyst,
but the continuous injection of small amounts of citric acid helps to prevent the formation of by-
products in excessive quantities. As for the operating conditions, the temperature is 110 to 130°C,
pressure 3 to 3.5x106 Pa absolute and residence time about 7 h for a once-through isobutane
conversion of 35 percent. The total yield of hydroperoxide and alcohol is 94 molar percent, and
the molar ratio of these two products is approximately 1.2. [2]
15 | P a g e
The make-up and recycle oxygen are introduced into the reactor with fresh and recycled isobutane
in a proportion such that the oxygen concentration is kept at less than 8 percent volume. It is
essential to ensure that this concentration remains below the lower flammability limit. Make-up
inert gas may be required to control this concentration.
The heat liberated by the conversion is removed by the vaporization of part of the reaction medium,
this method serves to concentrate the reaction stream by minimizing the thermal decomposition of
the peroxidic components, and by avoiding the need for cooling cycles which require large
investments and are big energy consumers, to condense the isobutane. [2]
Epoxidation of Propylene
Epoxidation takes place in the liquid phase. The catalyst employed for the purpose is generally a
5 percent weight solution of molybdenum naphthenate in a mixture of t-butyl hydroperoxide and
alcohol. The metal concentration in the reaction medium is about 0.05 per cent weight. Operations
take place between 80 and 110°C, at 3 to 4x106 Pa absolute, in a series of staged reactors, in the
presence of excess propylene (peroxide/alcohol/ propylene molar ratio 1/1/3). Residence time
ranges from 0.5 to 1 h per stage, and total residence time is about 2.5 h. It is about 1 h in the first
stage and 50 per cent of the hydroperoxide reacts. Once-through conversion of propylene reaches
15 per cent, and that of the hydroperoxide 90 to 95 percent. Molar selectivity of propylene oxide
and alcohol amount to 85 and nearly 95, percent respectively in relation to the peroxide. The heat
of reaction (∆H at 25oC = - 225 kJ/mol) is removed for the first reactor, by cooling a sidedrawal
stream that is recycled and, in the remaining four reactors, combined in a single shell, by
intermediate cooling in each stage, the temperature is 80°C at the inlet and 100°C at the outlet. [2]
The stream from the reaction section is first distilled to remove unconverted propylene, whose
recycle, added to the make-up, represents the feed of the first epoxidation stage. Excess propane
is also removed by distillation (50 to 60 trays) to prevent its buildup in the synthesis loop. The
heavy end of the first column is sent to the purification train for products for which the
temperatures cannot exceed 100°C to avoid undesirable degradation. On account of the boiling
points at standard pressure of the components present, this makes operation under vacuum
necessary. Crude propylene oxide is collected at the top of the first distillation column (50 trays),
and t-butyl alcohol at the bottom, with some hydroperoxide, the catalyst, propylene glycol,
aldehydes, esters etc. This stream is sent to a t-butyl alcohol separation column (35 to 40 trays),
16 | P a g e
where the alcohol is recovered at the top. The crude propylene oxide is subjected to extractive
distillation by means of a hydrocarbon (octane for example) in a set of two columns, one for
extraction (30 trays), and the second for solvent regeneration (15 trays). The extract is rid of light
products (50 trays) and heavy products (75 to 80 trays) to yield propylene oxide meeting
commercial specifications. [2]
The t-butyl alcohol, co-product produced at the rate of 2.5-3.5 kg/kg of propylene oxide [3],
depending on whether or not a market is available, is utilized as such or dehydrated to isobutene
(200°C, atmospheric pressure, titanium oxide base catalyst). If the isobutene is itself unusable, it
can be hydrogenated to isobutane, which is recycled. The good anti-knock properties of t-butyl
alcohol currently make it a highly popular additive for automotive gasolines. In addition, certain
recent processes (Mitsubishi Rayon, Nippon Shokubai, Oxirane) can be used to convert the t-butyl
alcohol to methacrylic acid.
Ethylbenzene Hydroperoxide Process
An important advantage of the process is that the coproducts from epoxidation have appreciable
economic values.
Epoxidation of propylene with ethylbenzene hydroperoxide is carried out at approximately 130°C
and 35 atmospheres in presence of molybdenum catalyst. A conversion of 98% on the
hydroperoxide has been reported
The coproduct α-phenylethyl alcohol could be dehydrated to styrene. Ethylbenzene hydroperoxide

is produced by the uncatalyzed reaction of ethylbenzene with oxygen: [2]
C H CH CH + O + C H CH(CH )OOH
In this process, involving the indirect oxidation of propene to propylene oxide, ethylbenzene (in
its hydroperoxide form) can be used as an auxiliary oxidation system. After being converted into
methylphenylcarbinol, it is dehydrated to styrene. About 2.2-2.5 kg styrene is obtained per
kilogram propylene oxide [3]. Currently, about 15% of the styrene produced worldwide is made
with this process. [2]
17 | P a g e
Other Indirect Oxidation Processes
Some of the other indirect oxidation processes are as follows: [4]

Table 2-1 Other Indirect Oxidation Processes
Starting Material Per-oxidizing Agent Co-Oxidized Substance Secondary Products
Acetaldehyde Acetic Acid or Anhydride _
Isobutane Tert-Butanol Isobutane, MIBK, or
methacrylic acid
Isopentane Isopentanol Isopentene and isoprene
Cyclohexane Cyclohexanone/ol _
Ethylbenzene Methylphenylcarbinol Styrene
Cumene Dimethylphenylcarbinol α-Metylstyrene
2.3. Direct Oxidation Processes
In theory, it should be possible to obtain PO through direct oxidation of propene with oxygen,
similarly to the industrial production of ethene oxide: [5]
C H + 1/2 O → C H O
The challenge in the case of propene oxidation is to find a catalyst that gives sufficiently high
selectivity for PO by suppressing the competing combustion reaction. The catalysts and reaction
conditions employed for the gas-phase epoxidation of ethene with molecular oxygen are not
suitable for carrying out epoxidation of higher olefins, such as propene [6]. In fact, the rate constant
for the complete oxidation of PO is negligible, but the rate of the complete oxidation of propene
is very high, being almost ten-fold faster than the complete oxidation of ethene. In contrast, the
epoxidation reaction of propene is almost ten-times slower than the epoxidation reaction of ethene.
All these factors lead to a poor selectivity for PO. [5]
18 | P a g e
Plant design for the direct oxidation of propene would most likely be based on pure oxygen feed,
rather than air, to gain yield advantage and lower capital costs. The minimal purge gas flow in an
oxygen-based process makes it economically feasible to use a ballast gas (diluent) other than
nitrogen. [5]
The gas-phase epoxidation of propene can be carried out on catalysts substantially similar to those
used for ethene epoxidation [7], when small amounts of either a nitrogen oxide species (NO, NO 2)
or a volatile organic chloride (ethyl chloride) are added to the feed stream [8]. However, the
addition of organic chlorides has disadvantages, such as an increase in the cost of raw materials,
and the necessity to recover chlorides in the exit stream (these recovery treatments generate
corrosive effluents).
2.4. Hydrogen Peroxide Process (HPPO)
Since each of the commercial processes has issues of effluent treatment, by-product treatment, co-
product sales, and cost, development of alternative processes that address one or more of these
issues is on-going.
C H +H O → C H O+H O
A titanium silicalite catalyst (TS-1) is used to produce propylene oxide from propylene and
hydrogen peroxide. Alcohol or alcohol–water mixtures are used as solvent. Methanol is the
preferred alcohol. Yields on peroxide are quantitative and propylene selectivity is high. TS-1 is a
molecular sieve catalyst. [9]
Using hydrogen peroxide for the manufacture of propylene oxide means that water is co-produced
in the reaction and no by-product needs to be disposed of or utilized. The reaction is carried out in
a dilute solution of hydrogen peroxide in aqueous methanol, below 60 oC and moderate pressure.
The reaction is fast even with ≤ 1% H2O2. The hydrogen peroxide process is characterized by
lower environmental impact, a simpler process scheme and lower investment. However, hydrogen
peroxide is relatively expensive and still produced in plants with relatively low nameplate
capacities. [10]
Compared to existing PO process technologies, HPPO is claimed to offer unique benefits from
economic and environmental points of view. New PO plants built using HPPO technology are
claimed to be more economical because they require up to 25% less capital. The simplicity of the
19 | P a g e
process derives from the fact that there is no need for additional infrastructure or markets for
coproducts, and also because a simpler raw material integration is required. The environmental
benefits derive from the reduction of wastewater by up to 70–80% and of energy usage by 35%.[5]
2.5. Patented Silver-Based Catalyst Process
Conventional industrial production of PO has many drawbacks. Two general approaches are taken
for PO production including the hydrochlorination route and the co-oxidation of propylene. The
traditional hydrochlorination route converts propylene to chloropropanols which are then
dehydrochlorinated to create PO. The chlorinated byproducts of this process, both organic and
inorganic salts, must be disposed of. The co-oxidation of propylene produces coproducts t-butyl
alcohol and styrene, which can decrease the economic benefit of producing PO. As a result of these
drawbacks, there has been extensive industry research on direct oxidation of propylene to make
PO with high selectivity for reduced byproduct production. [11]
The focus of this process is to make propylene oxide from propylene via direct oxidation to match
the demand. The reactor feed streams are 95% pure (chemical grade) propylene and 99.6% pure
oxygen. The reference patent from the Council of Scientific and Industrial Research (CSIR) gives
a laboratory selectivity of 100%. For industrial application, we assumed a 99.9% selectivity with
other compounds being created including CO 2, acetaldehyde, acrylic acid, and acrolein. However,
to make this process highly selective and produce propylene oxide at 99.9% selectivity a newly
patented catalyst is used. There is no such catalyst used for industrial scale production today. A
team of scientists from the Council of Scientific and Industrial research (CSIR) have applied for a
patent for a catalyst (silver oxide [Ag2O] supported on tungsten trioxide oxide [WO3]). The
laboratory research of CSIR for the catalyst is used as the basis of the design project. [11]
The direct oxidation of propylene is a very exothermic reaction, and the reactor is cooled down by
running boiler feed water through the shell side of the shell and tube reactor to produce steam.
Once propylene oxide is produced, the main byproduct (CO 2) needs to be separated through
adsorption. Monoethanolamine (MEA) is used as a solvent. Propylene oxide needs to be separated
from acetaldehyde, acrylic acid, and acrolein. The purity of the final product is under the purity
requirements of industry leaders and can be distributed to the entire PO market. [11]
20 | P a g e
Table 2-2 Comparison of Propylene Manufacturing Processes

Process Name Chlorohydrin Process T-butyl Hydroperoxide Ethylbenzene Hydrogen Peroxide Direct Oxidation using
Process Hydroperoxide Process Patented Silver based
Process Catalyst
Reactants: Propylene Propylene Propylene Propylene Propylene

Chlorine Isobutane Ethylbenzene Hydrogen Peroxide Oxygen
Water Oxygen Oxygen Methanol (Solvent)
Ca(OH)2 or NaOH
Steps: Chlorohydrination Production of Production of Single Step Process Single Step Process
Dehydrochlorination hydroperoxide hydroperoxide
Epoxidation of propylene Epoxidation of
propylene
Catalysts: None Solution of molybdenum Molybdenum (For titanium silicalite silver oxide [Ag2O]
naphthenate (For epoxidation step) catalyst (TS-1) supported on tungsten
epoxidation step) trioxide oxide
Intermediate: Propylene chlorohydrin t-butyl hydroperoxide Ethylbenzene None None
Hydroperoxide
By Product: 1,2-dichlorohydrin t-butanol α-phenylethyl alcohol Water Minor amount
Di-isopropyl ether That can be dehydrated
CaCl2 or NaCl to:
Styrene
Operating T = 35-40 oC T = 110-130 oC T = 130 oC T = 40-60 oC T = 350 oC
Conditions: P = 1-3 bar P = 30-35 bar P = 35 bar P = 20-30 bar P = 30 bar
Remarks: Oldest method Co-Product Process Co-Product Process Hydrogen peroxide Selectivity is 100%
1.4-1.5 kg of Cl is lost as price is high (performed on lab)
CaCl2 per Kg of Propylene 2.5-3.5 kg of t-butanol is 2.2-2.5 kg of styrene is
oxide produced per Kg of produced per Kg of Produces water as only Direct Oxidation
Propylene oxide Propylene oxide by product Process
waste disposal of CaCl2
Technically simple
Waste water treatment is epoxidation
required
21 | P a g e
2.6. Process Selection
Hydrogen Peroxide Process (HPPO) is selected due to the following reasons:

 Single step process
 Low temperature
 No By-Products
 Waste water is easy to purify
 Environment friendly
 The investment costs required for the HPPO technology are also lower
 Efficient raw material consumption
2.7. Rate Laws
The rate of reaction is given as:

. .
−𝑟 = 𝑘𝐶 𝐶
The orders with respects to hydrogen peroxide and propylene are 0.71 and 0.29 respectively. [12]
Overall order is 1
The activation energy is 46.36 kJ/mol. [13]
2.8. Effects of Parameters and Their Selection
Following are the effects of parameters:

Effect of Methanol (Solvent)
 It is known that methanol is best solvent for the epoxidation of propylene.

 the reaction rate and propylene oxide selectivity increased with the rising methanol
concentration, but did not change appreciably when the methanol concentration increased
from 65 to 70 %. [12]
 When the methanol concentration exceeded 65 wt. %, the reaction rate did not change
appreciably.
22 | P a g e
Therefore, 65 wt. % is the suitable concentration for the reaction.

Effect of Pressure
 The reaction rate decreased with the rising pressure, but propylene oxide selectivity
increased slightly.
 In addition, the reaction rate did not change appreciably after the pressure increased from
2.5 MPa to 3 MPa. [12]
Therefore 2.5 MPa will be suitable pressure for the reaction.

Effect of Temperature
 The reaction rate increased with the increasing temperature.

 However, the propylene oxide selectivity decreased, which led to the reduction of the
propylene oxide production rate.
 Especially, when the reaction temperature increased from 45 and 50 °C, the propylene
oxide selectivity changed obviously, indicating that more propylene glycol and alkyl ether
of propylene glycol was produced in this temperature range. [12], [14]
Therefore 40 OC will be suitable temperature for the reaction.
Figure 2-1 Effect of Temperature on Selectivity
23 | P a g e
Process Flow Diagram
P (Pump) St-101 (Stripper)

HX (Heat Exchangers) DC-101 (Propylene Oxide Distillation)
MIX (Mixer) DC-102 (Methanol-Water Distillation)
1 4 R-101 (Epoxidation Reactor) CD (Condenser)
7 FC-101 (Flash Column)
P-101 HX-101 RB (Reboiler)
VLV (Valve)
2 5 8 10
P-102 HX-102
9
3 6 MIX-101
P-103 HX-103
15
13
CD-101
17 CD-102
R-101
19
11 12 St-101 DC-101
FC-101
VLV-101
DC-102
14
16
P-104 RB-101 RB-102 18
P-105
RB-103 20
P-106
24 | P a g e
2.9. Process Description
Process Overview
Propylene oxide is manufactured through different technology. One of the major and latest
technology which is HPPO technology which uses Solid Titanium Silicate catalyst (TS-1) in the
packed bed reactor [12]. So, the major objective of this project is to produce the 100-metric ton
per day of propylene oxide through HPPO technology. Raw material is introduced into the reactor
in liquefied form under specified condition. The product is produced with the selectivity of
propylene oxide is 97% [5] and selectivity of propylene glycol is 3%. Here we ignored the other
by-products as they are formed in negligible amount. A simplified process flow diagram is shown
above. The reactor is fed with reactants along with the solvent. After the reaction the residual
propylene is separated in other recovery unit. The remaining product stream is lead to a separation
unit, where propylene oxide is separated from a water solvent mixture. The resulting propylene
oxide is very pure. The remaining solvent/water mixture is purified and recycled. The recycled
propylene as well as the purified solvent is lead back to the reaction mixture enabling integrated
solvent recycling leaving only water as a byproduct.
Raw Material
The raw material stream which is basically required for the production of Propylene oxide through
HPPO technology are given below:
 Polymer graded Propylene
 Hydrogen peroxide (50% solution)
 Methanol (pure)
Products and By-Products
 Propylene Oxide
 Propylene Glycol
 1-methoxy propanol (negligible)
 2-methoxy propanol (negligible)
25 | P a g e
Catalyst
The catalyst used in the HPPO technology is a micro porous titanium silicalite-1(TS-1). A typical
TS-1 synthesis starts with the dissolution of a silica (SiO 2) and a titanium source in the presence
of an organic template [15]. The powder needs to be designed for an application in fixed bed
reactors. The physical and chemical properties of these formed catalyst particles have a
considerable effect on the catalytic performance in the HPPO process. Titanium silicalite (TS-1)
catalyst promote the formation of propylene oxide with a high selectivity and a high hydrogen
peroxide conversion. There are several factors, having an impact on the catalytic performance. The
activation energy of the epoxidation is with 46.36 kJ/mol [13]. Therefore, a certain temperature
has to be applied to achieve the productive conversion.
Reaction Details
The reaction temperature is 40°C [12]. On the other side the epoxidation is an exothermic reaction
generating high which lower the propylene oxide selectivity due to side reaction, the ring opening
of propylene oxide to glycol or glycol ethers is the major side reaction. An optimized balance
between H2O2 conversion and propylene oxide selectivity using a fixed bed reactor. Running the
process at isothermal temperature, could obtain almost full conversion while keeping the
selectivity very high. Following are the reactions:
C H + H O → C H O + H O (Main Reaction)
C H O + H O → C H O + H O (Side Reaction)
C H O + CH OH → C H O (Side Reaction) (Negligible)
H O → 0.5O + H O (Decomposition Reaction) (Negligible)
2.10. Detailed Process Description
Feed Preparation
Propylene is usually transported and stored in liquid form at room temperature [16]. So, it was
assumed that propylene was fed to the process at 25℃ and 12.5 atm. It is then pumped to the
desired pressure. Similarly, hydrogen peroxide solution and solvent (methanol) at 1 atm and 25 ℃
are separately pumped and heated to the desired pressure and temperature respectively. The raw
material is introduced into the mixer along with solvent (methanol) in order to make it for the feed
26 | P a g e
of reactor at pressure of 25 atm. The propylene supplied is polymer grade. If chemical grade
propylene is taken, then an additional equipment should be installed to remove propane form
propylene.
Reactor
The reactor is the core of the process design as the desired product, propylene oxide, is produced
in this unit. Propylene oxide was produced by reacting propylene with liquid hydrogen peroxide
over a solid titanium silicate 1 (TS-1) catalyst in methanol-water solvent. The liquid-liquid reaction
system was chosen based on the kinetics obtained [12]. A packed bed reactor was chosen due to
the presence of catalyst and the nature of the reaction. The reaction rate for a packed bed reactor
is based on the weight of the catalyst as the reaction occurs on the surface on the catalyst. This
reactor has the highest conversion. The feed flow rates were obtained from the mass balance to
achieve the target production rate of 100 metric tons/day of propylene oxide. The epoxidation
reaction usually occurs between a temperature range of 40-60 ℃ and pressure range of 20-30 atm
over TS-1 catalyst in packed bed reactor with a catalyst diameter and void fraction of 1 mm [12]
and 0.34 [17] respectively. The reaction conditions 40℃ and 25 bar were chosen to avoid
decomposition of hydrogen peroxide and formation of by-products. The decomposition produces
oxygen leading to an explosive reaction with propene and a reduction of hydrogen peroxide
selectivity to propylene [18]. The selectivity of PO in the reactor is 97% [5]. The reactor should
be operated isothermally by removing heat continuously to prevent side reactions.
Pre-Separation Section
The effluents of reactor involve propylene oxide, propylene and remaining amount of water,
Hydrogen peroxide and Methanol. In this section usually, flash vessel is used to separated
unreacted propylene from propylene oxide, water, Hydrogen peroxide and Methanol. The pressure
is reduced from 25 atm to 1.75 atm by using throttling valve hence the unreacted propylene is
separated and recycled. In the flash vessel, 1/3 of unreacted propylene is separated.
The liquid stream from bottom of the flash vessel is sent to stripper to separate the remaining
propylene. Both the outputs of flash vessel and stripper are sent to purification unit from where
they are recycled back.
27 | P a g e
Propylene Oxide Distillation Column
The liquid stream from bottom of the stripper now contains propylene oxide, methanol and water.
It is sent to propylene oxide distillation column where the polymer grade propylene oxide is
separated at the distillate.
Methanol-Water Distillation Column
The liquid stream from bottom of the propylene oxide distillation column now contains methanol
and water. It is sent to methanol-water distillation column where methanol is separated from the
water at the distillate and recycled back to use as a solvent again, leaving behind only water as a
byproduct at the bottom of the distillation column.
References
[1] D. L. Burdick and W. L. Leffler, Petrochemicals in Nontechnical Language. PennWell

Corporation, 2010.
[2] A. Chauvel and G. Lefebvre, Petrochemical Processes (no. 3). Editions OPHRYS, 2001.
[3] Ullmann's Encyclopedia of Industrial Chemistry, 40 Volume Set. Wiley, 2011.
[4] K. Weissermel and H.-J. Arpe, Industrial organic chemistry. John Wiley & Sons, 2008.
[5] F. Cavani, G. Centi, S. Perathoner, and F. Trifirò, Sustainable Industrial Chemistry:
Principles, Tools and Industrial Examples. Wiley, 2009.
[6] T. A. Nijhuis, M. Makkee, J. A. Moulijn, and B. M. Weckhuysen, "The production of
propene oxide: catalytic processes and recent developments," Industrial & engineering
Chemistry research, vol. 45, no. 10, pp. 3447-3459, 2006.
[7] P. Hayden, Sampson, R.J, "US Patent 4,007,135 ", 1977.
[8] C. R. Hayden P., Ramforth, J.R. and C. A. F. , " US Patent 5,387,751," 1995.
[10] G. P. Chiusoli and P. M. Maitlis, Metal-catalysis in Industrial Organic Processes. RSC
Publishing, 2008.
[11] E. W. Schultz, M. B. Schwartz, and K. M. Yu, "Production of propylene oxide from
propylene using patented silver based catalyst," 2016.
28 | P a g e

[13] A. Sulimov, S. Danov, A. Ovcharova, A. Ovcharov, and V. Flid, "Kinetics of propylene
epoxidation with hydrogen peroxide catalyzed by extruded titanium silicalite in methanol,"
Kinetics and Catalysis, vol. 57, no. 4, pp. 466-473, 2016.
[14] M. Lin, C. Xia, B. Zhu, H. Li, and X. Shu, "Green and efficient epoxidation of propylene
with hydrogen peroxide (HPPO process) catalyzed by hollow TS-1 zeolite: A 1.0 kt/a pilot-
scale study," Chemical Engineering Journal, vol. 295, pp. 370-375, 2016.
[15] G. Xiong, D. Hu, Z. Guo, Q. Meng, and L. Liu, "An efficient Titanium silicalite-1 catalyst
for propylene epoxidation synthesized by a combination of aerosol-assisted hydrothermal
synthesis and recrystallization," Microporous and Mesoporous Materials, vol. 268, pp. 93-
99, 2018.
[16] A. K. Coker, Petroleum Refining Design and Applications Handbook, Volume 2: Rules of
Thumb, Process Planning, Scheduling, and Flowsheet Design, Process Piping Design,
Pumps, Compressors, and Process Safety Incidents. Wiley, 2021.
[17] P. Mehrani, Particles and Multiphase Systems. Ottawa, 2016.
[18] V. Russo, R. Tesser, E. Santacesaria, and M. Di Serio, "Kinetics of propene oxide
production via hydrogen peroxide with TS-1," Industrial & Engineering Chemistry
Research, vol. 53, no. 15, pp. 6274-6287, 2014.
29 | P a g e
CHAPTER 3: LAW OF CONSERVATIONS
3.1. Conservation of Mass
Introduction
The general conservation equation for any process system can be written as: [1]
𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑜𝑢𝑡 = 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐼𝑛 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 − 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛
For a steady state process, the accumulation term will be zero. Apart from nuclear processes, matter
is neither created nor consumed; but if a chemical reaction occurs, a chemical species may be
formed or consumed in the process. If no chemical reaction occurs, the steady state equilibrium
will decrease to
𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑜𝑢𝑡 = 𝑀𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝐼𝑛
A balance equation can be written for each separately identifiable species, elements, compounds,
or radicals present; and for the total material.
Basis for Calculations
100 MTPD of Propylene Oxide

Material Balance Across Reactor
Basis: 100 MTPD of Propylene Oxide = 4166.67 kg/hr

 Conversion of main reactant (Hydrogen Peroxide) to PO = 98% [2]
 Selectivity of Propylene Oxide = 97% [2]
 Extra margin for further separation = 96%
 Amount of Hydrogen Peroxide required for reaction = 2673.935 kg/hr
 50% Solution of Hydrogen Peroxide with Water [3]
 Amount of water = 2673.935 kg/hr
 Total Solution = 5347.87 kg/hr
 Methanol used will be 65% of hydrogen peroxide solution [4]
 Amount of methanol = 9931.758 kg/hr
 Propylene molar with respect to hydrogen peroxide ratio for maximum conversion will be
2:1 [3]
30 | P a g e
 Moles of Hydrogen Peroxide = 78.61 kmols/hr

 Moles of Propylene = 157.22 kmols/hr
 Mass of propylene = 6616.208 kg/hr
 Purity of propylene = 99.5% [5]
 Amount of propane = 33.081 kg/hr
Reactor In Reactor Out

Moles Mass Moles Mass
Component (kmols/hr) M.W (kg/hr) Component (kmols/hr) M.W (kg/hr)
H 2O 2 78.61 34.01 2673.93 H 2O 2 1.57 34.01 53.48
C3H6 157.23 42.08 6616.21 C3H6 80.19 42.08 3374.27
C3H8 0.75 44.10 33.08 C3H8 0.75 44.10 33.08
CH4O 309.96 32.04 9931.76 CH4O 309.96 32.04 9931.76
H 2O 148.43 18.02 2673.93 H 2O 223.16 18.02 4020.18
C3H6O 0.00 58.08 0.00 C3H6O 74.73 58.08 4340.28
C3H8O2 0.00 76.10 0.00 C3H8O2 2.31 76.10 175.87
694.98 21928.92 692.67 21928.92
IN (kg/hr) OUT (kg/hr)

21928.92 21928.92
Figure 3-1 Reactor (R-101) Mass Balance
Material Balance Across Flash Column
Following are the steps: [6]

 Use the Antoine equation to find the 𝑃 of each component
𝐵
𝑙𝑜𝑔 𝑃 = 𝐴 −
𝑇+𝐶
 Calculate the Bubble pressure
𝑧 =𝑥 𝑃 = ∑𝑃 𝑥
 Calculate the Dew Pressure
𝑧 =𝑦 𝑃 =∑
/
 Now, Calculate the amount and fraction of each component in vapor and liquid phase at
the operating pressure
31 | P a g e
𝐾 =𝑃 /𝑃
∑ =1 Where, 𝐿 + 𝑉 = 1
( )
 Component i in Top Product 𝑦𝑉

 Component i in Bottom Product 𝑥𝐿
Preliminary Information
Following are the values of Antoine Constants [7]:
Table 3-1 Antoine Constants
Component A B C
H2O2 8.0748 1958.1824 226.8000
C3H6 7.0072 859.7220 255.8950
C3H8 7.0202 889.8642 257.0840
CH4O 8.0840 1580.4585 239.0960
H2O 8.0557 1723.6425 233.0800
C3H6O 7.1453 1155.5706 236.2200
C3H8O2 8.0397 2015.9124 203.9120
Calculation:
By using the method [6] following are the calculations:
Table 3-2 Bubble Pressure calculation
Component PSat (mmHg) PSat (kPa) zi = xi xi*PSat

H2O2 5.4372 0.7249 0.0023 0.0016
C3H6 12640.1759 1685.2182 0.1158 195.0857
C3H8 10589.8890 1411.8691 0.0011 1.5291
CH4O 263.7926 35.1695 0.4475 15.7380
H2O 55.4461 7.3922 0.3222 2.3816
C3H6O 915.9562 122.1174 0.1079 13.1748
C3H8O2 0.5954 0.0794 0.0033 0.0003
∑ xi = 1
Pbubl =∑PSat xi =227.9111 kPa
32 | P a g e
Table 3-3 Dew Pressure calculation
Component zi = y i yi/PSat ki
H2O2 0.0023 0.0031 0.0041
C3H6 0.1158 0.0001 9.6298
C3H8 0.0011 0.0000 8.0678
CH4O 0.4475 0.0127 0.2010
H2O 0.3222 0.0436 0.0422
C3H6O 0.1079 0.0009 0.6978
C3H8O2 0.0033 0.0420 0.0005
∑ yi = 1
PDew =1/( ∑ yi /PSat )= 9.7635 kPa
Table 3-4 Flash Pressure Calculations
Component yi = ziki/1+V(ki-1) xi = yi/ki

H2O2 0.0000 0.0024
C3H6 0.7981 0.0829
C3H8 0.0066 0.0008
CH4O 0.0934 0.4646
H2O 0.0142 0.3370
C3H6O 0.0763 0.1094
C3H8O2 0.0000 0.0035
∑ yi = 1 ∑ xi = 1
33 | P a g e
Flash Column Top Product

Moles Mass
Component (kmols/hr) M.W (kg/hr)
H 2O 2 0.00 34.01 0.01
Flash Column In C3H6 25.81 42.08 1044.18
Moles Mass C3H8 0.20 44.10 9.03
Component (kmols/hr) M.W (kg/hr) CH4O 2.87 32.04 92.02
H 2O 2 1.57 34.01 53.48 H 2O 0.44 18.02 7.89
C3H6 80.19 42.08 3374.27 C3H6O 2.35 58.08 136.51
C3H8 0.75 44.10 33.08
C3H8O2 0.00 76.10 0.00
CH4O 309.96 32.04 9931.76
H 2O 223.16 18.02 4020.18 30.68 1289.65
C3H6O 74.73 58.08 4340.28
C3H8O2 2.31 76.10 175.87
Flash Column Bottom Product
Moles Mass
692.67 21928.92
z H 2O 2 1.57 34.01 53.47
C3H6 55.37 42.08 2330.08
C3H8 0.55 44.10 24.05
CH4O 307.09 32.04 9839.73
H 2O 222.72 18.02 4012.30
C3H6O 72.38 58.08 4203.77
C3H8O2 2.31 76.10 175.87
661.99 20639.27
21928.92 21928.92
Figure 3-2 Flash Column (FC-101) Mass Balance
Mass Balance Across Stripper
 Propylene is the light key

 Propylene oxide is the heavy key
 Percentage required of propylene in the distillate is 99%
 Percentage required of propylene oxide in the bottom product is 99%
 Assuming all the heavy non-keys go to bottom
 Assuming all the light non-keys go to top
 Find the composition of other components
 Calculate the total amount of distillate
34 | P a g e
 Calculate the total amount of Bottom product
Calculations [8]
Stripper Top Product
Moles Mass
C3H6 55.32 42.08 2327.75
C3H8 0.54 44.10 24.03
Stripper Feed C3H6O 0.07 58.08 4.20
Moles Mass CH4O 0.00 32.04 0.00
Component (kmols/hr) M.W (kg/hr) H 2O 0.00 18.02 0.00
C3H6 55.37 42.08 2330.08 H 2O 2 0.00 34.01 0.00
C3H8 0.55 44.10 24.05 C3H8O2 0.00 76.10 0.00
C3H6O 72.38 58.08 4203.77
CH4O 307.09 32.04 9839.73 55.93 2355.98
H 2O 222.72 18.02 4012.30
H 2O 2 1.57 34.01 53.47
C3H8O2 2.31 76.10 175.87
Stripper Bottom Product
661.99 20639.27 Moles Mass
C3H6 0.06 42.08 2.33
C3H8 0.00 44.10 0.02
C3H6O 72.31 58.08 4199.56
CH4O 307.09 32.04 9839.73
H 2O 222.72 18.02 4012.30
H 2O 2 1.57 34.01 53.47
C3H8O2 2.31 76.10 175.87
606.05 18283.29

20639.27 20639.27
Figure 3-3 Stripper (ST-101) Mass Balance
Material Balance Across Distillation Column 1
 Propylene oxide is the light key

 Methanol is the heavy key
 Percentage required of propylene oxide in the distillate is 99%
 Percentage required of methanol in the bottom product is 99%
35 | P a g e

Distillation Top Product

Moles Mass
Calculations [8] Component (kmols/hr) M.W (kg/hr)
C3H6 0.06 42.08 2.33
C3H8 0.00 44.10 0.02
C3H6O 72.23 58.08 4195.36
CH4O 0.31 32.04 9.84
H 2O 0.00 18.02 0.00
H 2O 2 0.00 34.01 0.00
C3H8O2 0.00 76.10 0.00
Distillation Feed
Moles Mass
72.60 4207.56
C3H6 0.06 42.08 2.33
C3H8 0.00 44.10 0.02
C3H6O 72.31 58.08 4199.56
CH4O 307.09 32.04 9839.73 Distillation Bottom Product
H 2O 222.72 18.02 4012.30 Moles Mass
H 2O 2 1.57 34.01 53.47 Component (kmols/hr) M.W (kg/hr)
C3H8O2 2.31 76.10 175.87 C3H6 0.00 42.08 0.00
C3H8 0.00 44.10 0.00
606.05 18283.29 C3H6O 0.07 58.08 4.20
CH4O 306.78 32.04 9829.89
H 2O 222.72 18.02 4012.30
H 2O 2 1.57 34.01 53.47
C3H8O2 2.31 76.10 175.87
553.46 14075.73

18283.29 18283.29
Figure 3-4 Distillation Column (DC-101) Mass Balance
Material Balance Across Distillation Column 2
 Methanol is the light key

 Water is the heavy key
36 | P a g e
 Percentage required of methanol in the distillate is 99%

 Percentage required of water in the bottom product is 99%
Calculations [8] Distillation Top Product

Moles Mass
C3H6 0.00 42.08 0.00
C3H8 0.00 44.10 0.00
Distillation Feed C3H6O 0.07 58.08 4.20
Moles Mass
CH4O 306.47 32.04 9820.06
H 2O 0.22 18.02 4.01
C3H6 0.00 42.08 0.00
H 2O 2 0.00 34.01 0.00
C3H8 0.00 44.10 0.00
C3H8O2 0.00 76.10 0.00
C3H6O 0.07 58.08 4.20
CH4O 306.78 32.04 9829.89
306.77 9828.28
H 2O 222.72 18.02 4012.30
H 2O 2 1.57 34.01 53.47
C3H8O2 2.31 76.10 175.87 Distillation Bottom Product
Moles Mass
553.46 14075.73 Component (kmols/hr) M.W (kg/hr)
C3H6 0.00 42.08 0.00
C3H8 0.00 44.10 0.00
C3H6O 0.00 58.08 0.00
CH4O 0.31 32.04 9.83
H 2O 222.50 18.02 4008.28
H 2O 2 1.57 34.01 53.47
C3H8O2 2.31 76.10 175.87
226.69 4247.45

14075.73 14075.73
Figure 3-5 Distillation Column (DC-101) Mass Balance
37 | P a g e
Overall Balance
Figure 3-6 Overall Balance
Table 3-5 Overall Balance
Inputs Outputs
Stream 1 6649.29 Stream 13 1289.65
Stream 2 5347.86 Stream 15 2355.98
Stream 3 9931.76 Stream 17 4207.56
Stream 19 9828.28
Stream 20 4247.45
Total 21928.92 Total 21928.92
38 | P a g e
3.2. Conservation of Energy
Introduction
A general equation can be written for conservation of energy: [1]

Energy out = Energy In + Generation − Consumption − Accumulation
This is a statement of the first law of thermodynamics.
An energy balance can be written for any process step. A chemical reaction will produce energy
(exothermic) or consume energy (endothermic). For steady state processes, the accumulation of
both mass and energy will be zero. Energy can exist in many forms and this makes the energy
balance to some extent more complex than the material balance.
Energy Balance Across Heat Exchangers
Steps:
 Obtain the heat capacity coefficients
 Calculate the heat capacity at average temperature by using the following correlation
C (J/mol. K) = A + BT + CT + DT where T (K) [7]

 Calculate the temperature difference
 Calculate the heat duty by
Q = nC ∆T
Table 3-6 Heat Capacity Coefficients
Component A B C D Tmin (K) Tmax (K)

H2O2 -15.248 0.67693 -0.00149 1.2E-06 273 694
C3H6 54.718 0.34512 -0.00163 3.88E-06 89 328
C3H8 59.642 0.32831 -0.00154 3.65E-06 86 333
CH4O 40.152 0.31046 -0.00103 1.46E-06 176 461
H2O 92.053 -0.03995 -0.00021 5.35E-07 273 615
C3H6O 53.347 0.51543 -0.0018 2.78E-06 162 434
C3H8O2 118.614 0.67283 -0.00184 2.13E-06 214 563
39 | P a g e
Calculations [9]
P = 25 atm
25 oC 40 oC
H-1
Component n (kmol) Cp (J/mol K) Tf Ti nCp nCp∆T
C3H6 157.2255 118.3836 313 298 18612.93 279194
C3H8 0.7501 120.6082 313 298 90.47 1357.18
280551.1 kJ
77.93 kW
Figure 3-7 Energy Balance Across Heat Exchanger 1
P = 25 atm
25 oC 40 oC
H-2
H2O2 78.612 86.3102 313 298 6785.08 101776.30
H2O 148.4282 75.3971 313 298 11191.07 167866
269642.35 kJ
74.90 kW
P = 25 atm
25 oC 40 oC
H-3
CH4O 309.9606 80.57376 313 298 24974.69 374620.40 kJ
104.06 kW
40 | P a g e
Energy Balance Across Mixer
Assumption
 Mixer is operating at study state
 No energy loss to the surrounding during mixing
Calculations [10]
Component Q (kJ)
C3H6 279194
Component Q (kJ)
C3H8 1357.18
C3H6 279194
C3H8 1357.18
Component Q (kJ) H2O2 101776.30
H2O2 101776.30 H2O 167866
H2O 167866 CH4O 374620.40
Total 924813.86
Component Q (kJ) P = 25 atm
Q = 256.89 kW
CH4O 374620.40
MX-1Energy Balance
Figure 3-10 Mixer
Energy Balance Across Reactor

 Calculate the heat of reactants
 Calculate the heat of products
 Obtain the heat of formation coefficients
 Calculate the heat of formation of each coefficient by using the following correlation
∆H (kJ/mol) = A + BT + CT where T (K) [7]

 Calculating Heat of reaction at 25 OC by using heat of formation
∆𝐻 = ∑𝐻 (𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑𝐻 (𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) [10]

 Calculating heat of reaction at temperature T
41 | P a g e
∆𝐻 , = ∑∆𝐻 + ∆𝐻 + ∑∆𝐻 [10]

Table 3-7 Heat of Formation Coefficients
Component A B C Tmin (K) Tmax (K)

C3H6 36.3420 -0.0649 3.0496E-05 298.15 1000
C3H8 -81.4350 -0.0913 4.4695E-05 298.15 1000
CH4O -187.9900 -0.0497 2.1603E-05 298.15 1000
H2O -238.4100 -0.0122 2.7656E-06 298.15 1000
C3H6O -73.7590 -0.0757 4.0190E-05 298.15 1000
C3H8O2 -411.1900 -0.0859 4.2755E-05 298.15 1000
Calculations
Reactor In Reactor Out

o
Tf = 40 C = 313 K Tref = 25 oC = 298 K Tf = 40 oC = 313 K Tref = 25 oC = 298 K
P = 25 atm P = 24.7 atm
Component n Cp nCp∆T Component n Cp nCp∆T
(kmols/hr) (J/mol.K) (kW) (kmols/hr) (J/mol.K) (kW)
H 2O 2 78.61 86.31 28.27 H 2O 2 1.57 86.31 0.57
C3H6 157.23 118.38 77.55 C3H6 80.19 118.38 39.55
C3H8 0.75 120.61 0.38 C3H8 0.75 120.61 0.38
CH4O 309.96 80.57 104.06 CH4O 309.04 80.57 103.75
H 2O 148.43 75.40 46.63 H 2O 224.08 75.40 70.40
C3H6O 0.00 C3H6O 74.73 121.80 37.92
C3H8O2 0.00 C3H8O2 1.39 213.39 1.23
Total 694.98 256.89 Total 692.67 253.80
∆H = -5430.2 kW
Figure 3-11 Reactor (R-101) Energy Balance
42 | P a g e
Energy Balance Across Flash Column


 Calculate the heat of vaporization by using the following correlation
∆H (kJ/mol) = A(1 − T/T ) where T (K) [7]

 Calculate the bubble and dew temperature at the operating pressure
 Calculate the heat of flash column feed stream by using nC (T − T )
 Calculate the heat of flash column bottom stream by using nC (T − T )
 Calculate the heat of flash column top stream by using n[C (T − T ) + ∆H ]
Table 3-8 Heat of Vaporization Coefficients
Component A Tc N Tmin (K) Tmax (K)

C3H6 26.09 364.76 0.35 87.90 364.76
C3H8 26.89 369.82 0.36 85.44 369.82
CH4O 52.72 512.58 0.37 175.47 512.58
C3H6O 40.17 482.25 0.36 161.22 482.25
C3H8O2 80.70 626 0.29 213.15 626
H2O 52.05 647.13 0.32 273.16 647.13
H2O2 61.90 730.15 0.32 272.74 730.15
Bubble Temperature Calculation

Following are the steps for the Bubble Temperature calculation: [6]
 Take the z = x
 Calculate the Pv of each component using Antoine equation
B
log P = A − where, P(mmHg) and T(℃)
T+C
 Calculate the value of K of each component by using K = P v/P
 Calculate y of each component using y = Kx
43 | P a g e
 Iterate T until ∑y = 1
Dew Temperature Calculation

Following are the steps for the Dew Temperature calculation: [6]
 Take the z = y
 Calculate the Pv of each component using Antoine equation
B
log P = A − where, P(mmHg) and T(℃)
T+C
 Calculate the value of K of each component by using K = P v/P
 Calculate x of each component using x = y/K
 Iterate T until ∑x = 1
Flash Column Top Product
Tv = 40 oC = 313 K Tref = 25 oC = 298 K P = 1.75 atm
Calculations [10] Component n Cp ∆Hv n(Cp∆T+∆Hv)
(kmols/hr) (J/mol.K) (kJ/mol) (kW)
H 2O 2 0.0002 86.3102 51.9029 0.0000
C3H6 24.4300 118.3836 13.6162 110.3521
C3H8 0.2010 120.6082 14.2011 0.8895
CH4O 2.8006 80.5738 37.4631 30.8300
H 2O 0.4299 75.3972 42.4023 5.3207
C3H6O 2.3000 121.7959 27.8242 19.3556
C3H8O2 0.0000 213.3905 66.2374 0.0000
Flash Column In Total 30.1617 166.7478
Tf = 40 oC = 313 K Tref = 25 oC = 298 K
P = 24.7 atm
Component n Cp nCp∆T Flash Column Bottom Product
(kmols/hr) (J/mol.K) (kW)
Tf = 40 oC = 313 K Tref = 25 oC = 298 K
H 2O 2 1.57 86.31 0.57 P = 1.75 atm
C3H6 80.19 118.38 39.55 Component n Cp nCp∆T
C3H8 0.75 120.61 0.38 (kmols/hr) (J/mol.K) (kW)
CH4O 309.04 80.57 103.75 H 2O 2 1.57 86.31 0.56
H 2O 224.08 75.40 70.40 C3H6 55.37 118.38 27.31
C3H6O 74.73 121.80 37.92 C3H8 0.55 120.61 0.28
C3H8O2 1.39 213.39 1.23 CH4O 307.09 80.57 103.10
Total 692.67 253.80 H 2O 222.72 75.40 69.97
C3H6O 72.38 121.80 36.73
C3H8O2 2.31 213.39 2.05
Total 661.99 240.00
Figure 3-12 Flash Column (FC-101) Energy Balance
44 | P a g e
Energy Balance Across Stripper
Steps:

 Calculate the heat of vaporization by using the following correlation
∆H (kJ/mol) = A(1 − T/T ) where T (K) [7]

 Calculate the bubble and dew temperature at the operating pressure
 Calculate the heat of stripper feed stream by using nC (T − T )
 Calculate the heat of stripper bottom stream by using nC (T − T )
 Calculate the heat of stripper top stream by using n[C (T − T ) + ∆H
Calculations [10] Stripper Top Product

Tv = -34.75 oC = 238.25 K Tref = 25 oC = 273 K
Component n Cp ∆Hv n(Cp∆T+∆Hv)
(kmols/hr) (J/mol.K) (kJ/mol) (kW)
H 2O 2 0.00 86.3102 51.9029 0.0000
C3H6 55.32 118.3836 13.6162 206.3952
C3H8 0.54 120.6082 14.2011 2.0840
CH4O 0.00 80.5738 37.4631 0.0000
H 2O 0.00 75.3972 42.4023 0.0000
C3H6O 0.07 121.7959 27.8242 0.5157
Stripper Feed C3H8O2 0.00 213.3905 66.2374 0.0000
Tf = 40 oC = 313 K Tref = 25 oC = 298 K Total 55.93 208.9948
P = 1.75 atm
Component n Cp nCp∆T
H 2O 2 1.57 86.31 0.56 Stripper Bottom Product
C3H6 55.37 118.38 27.31 Tf = 83 oC = 356 K Tref = 25 oC = 298 K
C3H8 0.55 120.61 0.28 Component n Cp nCp∆T
CH4O 307.09 80.57 103.10 (kmols/hr) (J/mol.K) (kW)
H 2O 222.72 75.40 69.97 H 2O 2 1.57 88.29252 2.23331
C3H6O 72.38 121.80 36.73 C3H6 0.06 128.6275 0.12434
C3H8O2 2.31 213.39 2.05 C3H8 0 130.3361 0
Total 661.99 240.00 CH4O 307.09 82.67484 409.0388
H 2O 222.72 75.119 269.547
C3H6O 72.31 126.2977 147.1361
C3H8O2 2.31 216.6136 8.061636
Total 606.05 836.1412
Figure 3-13 Stripper (ST-101) Energy Balance
45 | P a g e
Energy Balance Across Distillation Columns

• Calculate the heat of feed stream by using ∆H = ∑nC ∆T
• Calculate the heat of distillate by using ∆H = ∑nC ∆T
• Calculate the heat of bottom product by using ∆H = ∑nC ∆T
• Calculate the heat of reflux liquid ∆H
• Calculate the heat of vapors at top of distillation column ∆H
• Calculate the condenser duty by Q = ∆H + ∆H − ∆H
• Calculate the reboiler duty by Q = (∆H + ∆H + Q ) − ∆H

Calculations
Tf = 50.55 oC = 323.55 K Tref = 25 oC = 298 K
Q = 648.46 kW (kmols/hr) (J/mol.K) (kW)
H 2O 2 0 86.8275 0
C3H6 0.06 120.7237 0.0514
C3H8 0 122.8316 0
Distillation Feed CH4O 0.31 81.0594 0.1783
Tf = 83 oC = 356 K Tref = 25 oC = 298 K H 2O 0 75.3038 0
P = 1.70 atm C3H6O 72.23 122.8304 62.9668
Component n Cp nCp∆T C3H8O2 0 214.1666 0
(kmols/hr) (J/mol.K) (kW) Total 72.6 63.1965
H 2O 2 1.57 88.29252 2.23331
C3H6 0.06 128.6275 0.12434
C3H8 0 130.3361 0 Distillation Bottom Product
CH4O 307.09 82.67484 409.0388 Tf = 89.91 oC = 362.91 K Tref = 25 oC = 298 K
H 2O 222.72 75.119 269.547
C3H6O 72.31 126.2977 147.1361 (kmols/hr) (J/mol.K) (kW)
C3H8O2 2.31 216.6136 8.061636 H 2O 2 1.57 88.5820 2.5076
Total 606.05 836.1412
C3H6 0 130.4547 0.0000
C3H8 0 132.0702 0.0000
CH4O 306.78 83.0449 459.3560
Q = 648.17 kW H 2O 222.72 75.1005 301.5860
C3H6O 0.07 127.0965 0.1604
C3H8O2 2.31 217.1500 9.0444
Total 533.45 772.6543
Figure 3-14 Distillation Column (DC-101) Energy Balance
46 | P a g e

Tf = 79.16 oC = 352.16 K Tref = 25 oC = 298 K
H 2O 2 0 88.1284 0.0000
C3H6 0 127.6345 0.0000
C3H8 0 129.3937 0.0000
Q = 635.86 kW CH4O 306.47 82.4733 380.2574
H 2O 0.22 75.1325 0.2487
C3H6O 0.07 125.8634 0.1325
C3H8O2 0 216.3182 0.0000
Distillation Feed Total 306.76 380.6387
Tf = 89.91 oC = 362.91 K Tref = 25 oC = 298 K
P = 1.65 atm
H 2O 2 1.57 88.5820 2.5076
C3H6 0 130.4547 0.0000
C3H8 0 132.0702 0.0000 Distillation Bottom Product
CH4O 306.78 83.0449 459.3560 Tf = 116.4 oC = 389.4 K Tref = 25 oC = 298 K
H 2O 222.72 75.1005 301.5860 Component n Cp nCp∆T
C3H6O 0.07 127.0965 0.1604 (kmols/hr) (J/mol.K) (kW)
C3H8O2 2.31 217.1500 9.0444 H 2O 2 1.57 89.6271 3.5726
Total 533.45 772.6543 C3H6 0 137.9570 0.0000
C3H8 0 139.1868 0.0000
CH4O 0.31 84.5594 0.6655
H 2O 222.5 75.1013 424.2493
C3H6O 0 130.3752 0.0000
Q = 685.19 kW C3H8O2 2.31 219.2714 12.8599
Total 226.69 441.3473
Figure 3-15 Distillation Column (DC-102) Energy Balance
References
[1] R. K. Sinnott, J. M. Coulson, and J. F. Richardson, Chemical engineering design (no. 4).
Elsevier Butterworth-Heinemann Oxford, 2005.
[2] F. Cavani, G. Centi, S. Perathoner, and F. Trifirò, Sustainable industrial chemistry:
Principles, tools and industrial examples. John Wiley & Sons, 2009.
[3] T. Haas, Hofen, W., Sauer, J. and Thiele, G. , "European Patent 1,373,235 and 1,373,236,"
2002.
47 | P a g e

[6] J. M. Smith, "Introduction to chemical engineering thermodynamics," ed: ACS
Publications, 1950.
[7] C. L. Yaws and C. Gabbula, Yaws" Handbook of thermodynamic and physical properties
of chemical compounds. Knovel, 2003.
[8] B. K. Dutta, Principles of mass transfer and seperation processes. PHI Learning Pvt. Ltd.,
2007.
[9] R. M. Felder, R. W. Rousseau, and L. G. Bullard, Elementary principles of chemical
processes. John Wiley & Sons, 2020.
[10] D. M. Himmelblau and J. B. Riggs, Basic principles and calculations in chemical
engineering. FT press, 2012
48 | P a g e
P (Pump) St-101 (Stripper)
49 | P a g e
HX (Heat Exchangers) DC-101 (Propylene Oxide Distillation)
MIX (Mixer) DC-102 (Methanol-Water Distillation)
1 4 R-101 (Epoxidation Reactor) CD (Condenser)
7 FC-101 (Flash Column)
P-101 HX-101 RB (Reboiler)
VLV (Valve)
2 5 8 10
P-102 HX-102
CHAPTER 4: EQUIPMENT DESIGN
9
3 6 MIX-101
P-103 HX-103
15
13
CD-101
17 CD-102
R-101
19
11 12 St-101 DC-101
FC-101
VLV-101
DC-102
14
16
P-104 RB-101 RB-102 18
P-105
RB-103 20
P-106
Stream No. 1 2 3 4 5 6 7 8 9 10
Temperature (oC) 25 25 25 25 25 25 40 40 40 40
Pressure (atm) 12.5 1 1 25 25 25 25 25 25 25
Phase Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid Liquid
Components
H2O2 0.00 2673.93 0.00 0.00 2673.93 0.00 0.00 2673.93 0.00 2673.93
C3H6 6616.21 0.00 0.00 6616.21 0.00 0.00 6616.21 0.00 0.00 6616.21
C3H8 33.08 0.00 0.00 33.08 0.00 0.00 33.08 0.00 0.00 33.08
CH4O 0.00 0.00 9931.76 0.00 0.00 9931.76 0.00 0.00 9931.76 9931.76
H2O 0.00 2673.93 0.00 0.00 2673.93 0.00 0.00 2673.93 0.00 2673.93
C3H6O 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
C3H8O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Total Mass flowrate (kg/hr) 6649.29 5347.86 9931.76 6649.29 5347.86 9931.76 6649.29 5347.86 9931.76 21928.92
Energy (kW) - - - 6.133 4.143 11.37 77.93 74.90 104.06 256.89
Stream No. 11 12 13 14 15 16 17 18 19 20
Temperature (oC) 40 40 40 40 -34.75 83 55.55 89.91 79.16 116.4

Pressure (atm) 24.7 1.75 1.75 1.75 1.7 1.75 1.7 1.65 1.6 1.7
Phase Liquid Mixture vapor Liquid vapor Liquid Liquid Liquid Liquid Liquid
Components
H2O2 53.48 53.48 0.01 53.47 0.00 53.47 0.00 53.47 0.00 53.47
C3H6 3374.27 3374.27 1044.18 2330.08 2327.75 2.33 2.33 0.00 0.00 0.00
C3H8 33.08 33.08 9.03 24.05 24.03 0.02 0.02 0.00 4.20 0.00
CH4O 9931.76 9931.76 92.02 9839.73 4.20 9839.73 9.84 9829.89 9820.06 9.83
H2O 4020.18 4020.18 7.89 4012.30 0.00 4012.30 0.00 4012.30 4.01 4008.28
C3H6O 4340.28 4340.28 136.51 4203.77 0.00 4199.56 4195.36 4.20 0.00 0.00
C3H8O2 175.87 175.87 0.00 175.87 0.00 175.87 0.00 175.87 0.00 175.87
Total Mass Flowrate (kg/hr) 21928.92 21928.92 1289.65 20639.27 2355.98 18283.29 4207.56 14075.73 9828.28 4247.45
Energy (kW) 253.80 253.80 166.75 240 208.99 836.14 63.19 772.65 380.64 441.35
50 | P a g e
4.1. Reactor Design
Chemical reactors are the most important features of a chemical process. A reactor is a part of the
equipment in which the raw material is transformed into the desired product. Various factors are
considered when selecting chemical reactors for specific tasks. In addition to economic cost, the
chemical engineer must select the correct reactor that will provide the highest yields and purity,
minimize pollution, and maximize profit. In general, reactors are chosen that will meet the
requirements set by reaction mechanisms, speed expressions and the required production capacity.
Other relevant parameters that must be determined to select the right type of reactor are the heat
of reaction, the reaction rate constant, the heat transfer coefficient, and the size of the reactor. The
reaction conditions must also be determined, including the temperature of the heat transfer
medium, the temperature of the feed reaction mixture, the composition of the feed, and the
instantaneous temperature of the reaction mixture. An important factor in reactor operation is the
output conversion rate. Operating conditions such as temperature, pressure and degree of mixing
are related to the most economical operation. [1]
Selection Criteria
Choosing the right reactor for the process is just as important as the exact temperature and pressure
conditions to carry out the reaction. The choice of reactor depends on the following factors: [2]
 Mode of Operation (batch, semi batch or continuous)
 Type of Flow
 Catalyst Bed (Fixed bed or fluidized bed)
 Reaction Phase (Homogeneous or heterogeneous catalysis)
Mode of Operation
In a batch reactor, the reaction contents are fed into the vessel at once and then removed some time
later. This is a closed system with mass, i.e. no mass can cross the boundaries of the container
during the reaction delay time. If certain reagents are fed into the vessel while processing a portion
of them, the reactor is called as semi-batch. A continuous reactor is a reactor that allows reagents
to enter and exit during the process. A comparison of batch and continuous process is given below: [2]
51 | P a g e
Table 4-1 Continuous Vs Batch Reactor
Parameters Continuous Reactor Batch Reactor

Rate of production High Low
Residence time Low High
Operating cost Low High
Temperature control Good Poor
Ease of automation Easy Difficult
Work force Low High
Continuous reactor is selected due to following reasons:

 100 MTPD production is required that is suitable for continuous reactor
 Low operating cost
 Good temperature control is required
Type of Flow
On the basis of interaction of the reagents in the reactor, the reactors are classified as: [2]
 Continuous Stirred Tank Reactor (CSTR)
 Plug Flow Reactor (PFR)
The CSTR is equipped with an impeller. One or more reagents, which may be solid or liquid, are
fed into the reactor. The impeller stirs the reaction mixture at a set rpm to ensure homogeneous
mixing. Unlike a CSTR, the reactants move in tubes without any axial mixing in a PFR. The tube
is divided into small segments, each segment is called a plug. A brief comparison of PFR and
CSTR is given below: [2], [3]
Table 4-2 Comparison of CSTR and PFR
Parameters Continuous Stirring Tank Plug Flow Reactor (PFR)

Reactor (CSTR)
Composition Uniform Varies along the length
Mixing Axial Perpendicular
Back mixing Maximum Minimum
Agitation Required Prohibited
Temperature Uniform Varies along the length
Pressure Suitable for low pressure Suitable for high pressure
Reactor Volume More Less (for same conversion)
Plug Flow Reactor is selected due to following reasons:

52 | P a g e
 No mixing is required
 Process pressure is high
 Heat transfer is required to operate the reactor isothermally
Catalysis
Catalysis can be of two types: [4]

 Homogeneous Catalysis
 Heterogeneous Catalysis
Homogeneous catalysis involves reactants and catalyst in the same phase. The product formed
after the reaction is also in the same phase. In other words, the entire reaction mixture is in the
same phase. In contrast, when the reactants and products differ in phase from the catalyst, the
reaction is said to be heterogeneous catalysis.
For this process reactants are in liquid phase and catalyst is in solid phase. So, Heterogeneous
Catalysis will be used.
Catalyst Bed
Industrially, there are two practices by which heterogeneous catalysis is carried out. The catalyst
bed can either be packed bed or fluidized bed. Reactors in which the solid catalyst particles remain
static at their position relative to other particles are the fixed bed particles. Whereas the reactors in
which the particles are suspended in the fluid, solely due to upward pressure of fluid are termed as
fluidized bed reactors. [5]
Table 4-3 Comparison of Fixed Bed Reactor and Fluidized Bed Reactor
Parameters Fixed Bed/Packed Bed Fluidized Bed
Contact Phases Solid-Liquid or Solid-Gas Solid-Gas

Operating cost Low High
Operating pressure High operating pressure 10-12 MPa
Residence time Less (leading to plug flow) High (leading to good mixing)
Pressure drop High Low
Catalyst handling No difficulty Technical difficulties
Catalyst loss No loss Possible
Supporting equipment Not required Required
53 | P a g e
Fixed Bed is selected due to the solid-liquid phase.

Packed Bed Selection
The catalyst pellets are contained in the reactor as shown in the figure below, in a single bed,
multiple beds in a single jacket, multiple filled tubes in a single jacket, or a single bed with
embedded tubes. Deviation from a simple single bed may be required due to the need to add or
remove heat, redistribute the flow to avoid channels, or limit the height of the bed to prevent
crushing of the catalyst. In all reactors shown in below Figure, the reaction fluid flows down the
bed instead of up to prevent fluidization and minimize catalyst entrainment in the outlet fluid. [5]
 The simplest packed reactor is the single-bed adiabatic reactor shown in Figure (a). It is
the most commonly used type of reactor. If the reactants must be cooled to reduce catalyst
fouling or deactivation, select one of the other reactor types.
 In the reactor shown in Figure (b), part of the feed stream is diverted and mixed with the
hot fluid from the upper bed before entering the lower bed. The methanol synthesis reactor
uses this method of cooling. Adding an excess of one of the reactants or an inert gas could
also reduce the temperature rise of the reactants. These gases are coolers, they absorb the
enthalpy of reaction.
 In the reactor shown in Figure (c), the catalyst is encased in tubes and a heat transfer fluid
flows through the jacket to add or remove heat. If the heat transfer fluid is water, then steam
can be generated for use in the process.
 Alternatively, the reacting fluids can be cooled by an internal and external cooler as shown
in Figure (d), and (e) respectively.
 In another arrangement, the feed gas cools the reaction gases, as shown in Figure (f). Here,
the feed gas is preheated in an external exchanger by cooling the feed gas, and then the
feed gas is further heated in the reactor by flowing upward, countercurrent to the downward
flow of hot reactants.
54 | P a g e
Figure 4-1 Different Types of Fixed/Packed Bed Reactor
Multi-Tubular Fixed Bed is selected due to the following reasons:

 High Temperature sensitivity
 Efficient Heat Transfer
 Ease of Operation
Hence the overall Reactor selected is:

Continuous, Multi-Tubular Fixed Bed, Heterogeneous Catalytic Plug Flow Reactor
Design Steps
 Specifying Reactor conditions
 Chemical Reaction Kinetic Data
 Calculation of volume of Reactor
 Calculation of Residence time
55 | P a g e
 Heat Transfer calculations (tube and shell side)
 Pressure drop across packed bed
Reaction Mechanism
𝐶 𝐻 + 𝐻 𝑂 → 𝐶 𝐻 𝑂 + 𝐻 𝑂 (𝑀𝑎𝑖𝑛 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
𝐶 𝐻 𝑂 + 𝐻 𝑂 → 𝐶 𝐻 𝑂 + 𝐻 𝑂 (𝑆𝑖𝑑𝑒 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
If the reaction temperature is maintained, the conversion and selectivity of the main reaction is
very high. Therefore, it will be suitable to use only the kinetics of the main reaction for the design.
Suitable Conditions:
 Temperature 40 oC  Pressure 25 atm
 Catalyst: Titanium Silicalite (TS-1)  Solvent: Methanol
Kinetics
The rate of reaction is given as: [6], [7]

. .
−𝑟 = 𝑘𝐶 𝐶
 The orders with respects to hydrogen peroxide and propylene are 0.71 and 0.29
respectively.
 Overall order is 1
 The activation energy is 46.36 KJ/mol
Rate Constant
k=k e [8]
 ko = 321 L/s.g =19260 L/min.g [7]  E= 46.36 kJ/mol  T= 40 oC = 313 K
 R= 0.008314 kJ/mol.K
Putting Values, k= 0.000353 L/min.g

Performance Equation
W dX W dX
= => =
F −r F kC C
56 | P a g e
Let C = C &C =C
W dX W dX
= => =
F kC C F k(C −C X ) (C −C X )
C X =C X
W dX
=
F k(C −C X ) (C −C X )
C
Let M =
C
W dX
=
F k(C ) (1 − X ) (M − X )
m + n = 0.71 + 0.29 = 1
W dX
=
F kC (1 − X ) . (M − X ) .
Graph
Conversion Vs 1/-r Graph

20000
15000
1/-r
10000
5000
0
0 0.33 0.66 0.99
Conversion (X)
Figure 4-2 Conversion Vs 1/-r Graph
Weight of Catalyst
From graph area under the curve:
57 | P a g e
dX
= 2657.44 g. min/mol
−r
dX
W= ×F
−r
min mol
W = 2657.44 g. × 1310.213 = 3481812 g
mol min
𝐖𝐞𝐢𝐠𝐡𝐭 𝐨𝐟 𝐜𝐚𝐭𝐚𝐥𝐲𝐬𝐭 = 𝟑𝟒𝟖𝟏. 𝟖𝟏𝟐 𝐊𝐠
Volume of Catalyst Bed
W
V =
ρ
ρ = 985kg/m [9]
3481.812 Kg
V = = 𝟑. 𝟓𝟑𝟓𝟑 𝐦𝟑
985kg/m
Volume of Reactor
V=
where ε= void fraction = 0.34 [10]

3.5353 m
V= = 5.3566 m
1 − 0.34
10 % excess for packing in tube [2]
V = 1.1 × 5.3566 m = 𝟓. 𝟖𝟗𝟐𝟑 𝐦𝟑
Residence Time
τ= [8]
v is the volumetric flow rate

5.8923 m
τ= = 𝟏𝟏. 𝟐𝟐𝟐𝟔 𝐦𝐢𝐧
0.5250 m /min
Number of Tubes Required
Pri
Tube wall thickness = + Cc [11]
SEj − 0.6P
58 | P a g e
P= Pressure(kPa) = 1.1(Operating pressure)

ri = inside radius(m)
S= Max allowable strength (kPa) =72400 (Stainless 304) [11]
Cc= Corrosion Allowance = 3mm [11]
Tubes dimensions [12]
Length of tubes [13]
Tube Dimensions
Table 4-4 Tube Selection
ID BWG Thickness OD Length Vtube = πDi2L/4 Nt

(in) (in) (in) (in) (in3) m3
1.67 8 0.165 2 144 315.2573 0.0052 1140.5657
1.67 8 0.165 2 192 420.3430 0.0069 855.4242
1.67 8 0.165 2 240 525.4288 0.0086 684.3394
2.64 7 0.18 3 144 787.8436 0.0129 456.3997
2.64 7 0.18 3 192 1050.4581 0.0172 342.2998
2.64 7 0.18 3 240 1313.0726 0.0215 273.8398
3.594 6 0.203 4 144 1460.1191 0.0239 246.2618
3.594 6 0.203 4 192 1946.8255 0.0319 184.6964
3.594 6 0.203 4 240 2433.5319 0.0399 147.7571
4.56 5 0.22 5 144 2350.5085 0.0385 152.9761
4.56 5 0.22 5 192 3134.0114 0.0514 114.7321
4.56 5 0.22 5 240 3917.5142 0.0642 91.7857
Assumed dimensions of tubes are:

 O.D (in) = 4  BWG = 6
 I.D (in) = 3.594  Thickness = 0.203 (in)
 Length (in) = 192  Volume of tube = 0.0319 m3
 No. of tubes = 185
Tube Side Heat Transfer Coefficient
Area available for Heat transfer

Aavailable = π × D × L × N = 237.4542 m2
59 | P a g e
πD
Flow Area per tube = A =
4
πD
Putting values, A = = 0.006542 m
4
Mass flow
Mass velocity = G =
Area
6.091
Mass velocity = G = = 5.0415 kg/m . s
0.006542 × 185
hd d G
= 3.6
k με
 Diameter of particle = d [6]  void fraction = ε
 viscosity = μ [14]  conductivity = k [14]
Putting values in the formula
h (0.001) (0.001)(5.0415)
= 3.6
(0.3119) (0.0005183)(0.34)
𝐰
𝐡𝐢 = 𝟑𝟖𝟏𝟖. 𝟗𝟔𝟔 𝟐
𝐦 𝐊
Shell Side Heat Transfer Coefficient
Cooling Medium: Water

Inlet temperature = 25 ºC Outlet Temperature = 35 ºC
Mass flow rate = m = = 129.7229 kg/s

∆
For triangular tube pitch =P = 1.25 × D =0.127 m [15]

.
D = equivalent Dia = (P − 0.907D )= 0.07326 m
/
D = Dia of tube Bundle = D = 1.9792 m
(Where, K1= 0.319, n1 = 2.142) [15]

Clearance = C = 0.0254m [13]
D = Dia of shell = D + C = 2.0053 m
B = Baffle spacing = 0.4 × D = 0.8021 m
No. of baffles = −1=5
60 | P a g e
[( )× × ]
Flow Area = A = = 0.3217 m2
Mass Velocity = G = 403.2217 kg/m2.s

×
Reynold No. = Re = = 36351.9 µ= 0.000813 Pa.s
µ
(j = 0.0064 for 25% cut baffles) [15]

×µ
Prandtl No. = Pr = =5.6098 k = 0.613 W/m.K
. µ .
h = j × Re × Pr × ( )
µ
𝐡𝐨 = 3439.22 W/m2.K
Overall Heat Transfer Coefficient
D
1 1 1 D ln D 1 D 1
D
= + + + × + × [13]
U h h D 2k D hD D h
K (S.S 304) = 16.2 W/m.K
For water Rd=0.00023 m2.K /W [13]
For organic liquids Rd= 0.0002 m2.K /W [13]
𝐔𝐨 =2298.584 W/m2 . K
Process 40℃
40℃
stream
35℃
25℃
Figure 4-3 Log Mean Temperature Difference
∆T − ∆T (40 − 35) − (40 − 25)

LMTD = = = 9.1023 ºC
∆T (40 − 35)
ln ( ) ln[ ]
∆T (40 − 25)
Area Required
Q
Area Required = A = = 259.53 m
U ∆T
Area Available > Area Required
61 | P a g e
(Aavailable − Arequired)
Excess Area = × 100% = 10.71%
Arequired
Excess Area must be > 10% [2]
So, assumed I.D was correct.
Length of shell = 1.2×(Length of tube) [2]
Length of shell = 5.8521 m
Pressure Drop on Tube Side
ΔP ηv (1 − ε) 7 ρv 1−ε
= 150 + [5]
L Dp2 ε 4 Dp ε
 η=0.000518 Pa.s  vs=0.006099 m/s
 L=4.8768 m  ε =0.34
After putting the values, we get, ∆𝑷 = 30.03 KPa

Pressure Drop on Shell Side
D LT Us μ .
∆P = 8 × f × × × ρ. × [13]
D Bs 2 μw
 f = fanning factor = 0.0433 [13]  U = 0.4032 m/s

 Bs = 0.8021 m  D = 0.025739 m
 D = 2.007325 m  Lt = 4.8768 m
 ρ = 1000kg/m
Putting Values, ∆Ps = 6.6540KPa < 68 Kpa
62 | P a g e
Specification Sheet of Reactor
Multi-tubular Fixed Bed, Heterogeneous Catalytic Plug Flow Reactor
Operation: Continuous
Orientation: Vertical
Catalyst
Titanium Silicalite (TS-1) Volume used: 3.5353 m3
Weight: 3481.81 kg Shape: Cylindrical
Shell and Tube Specifications
Tube Side Specifications Shell Side Specifications
Outer diameter: 0.1016 m, B.W.G 6 Shell inside diameter: 2.0053 m
Length of Tube: 4.8768 m Length of Shell: 5.8521 m
Heat Transfer Area Required: 259.53 m2
Residence Time: 11.2226 minute
Volume of Reactor: 5.8922 m3
Pressure Drop across Catalyst Packed Bed: 30.03 kPa
Material of construction: Stainless Steel (304) (both for tube and shell)
4.2. Flash Separator Design
Flash liquid vapor separators separate two-phase inputs into pure liquids and pure vapors. It mainly
helps in recovering valuable products and increasing the quality of products. [16]
Gas-Liquid Separators:
The separation of liquid droplets and mist from gas or vapor streams is analogous to the separation
of solid particles, and with the possible exception of filtration, the same techniques and equipment
can be used. Where carryover of some fine droplets can be tolerated, it is often sufficient to rely
on gravity settling in a vertical or horizontal separation vessel.
Types of Flash Separators
 Horizontal Phase Separator

 Vertical Phase Separator
 Spherical Phase Separator
63 | P a g e
Selection Criteria
Below table shows selection criteria [15], [17]

Table 4-5 Types of Separators
Horizontal Phase Separator Vertical Phase Separator Spherical Phase Separator
For large liquid volume For lesser liquid volume For smaller capacities
Easy gravity settling Comparatively difficult Lesser gravity settling
settling
Interface area is larger Smaller interface area Smallest interface area
Most efficient Comparatively lower efficient Less efficient
Most economical Less economical Very less economical
Horizontal phase separator is selected because vapor to liquid ratio is small.

Internals of Flash Separator
Splash Plate
 It is used to initiate the bulk separation of liquid and gas. It provides a means of causing a
sudden and rapid change in the momentum of the entering stream. If it is not present, the vapors
will escape very quickly without contacting any liquid to achieve equilibrium.
 Use a splash plate with the same thickness as the shell at a distance of 0.1524m in front of the
flash separator's inlet. [17]
Figure 4-4 Flash Column Internals

64 | P a g e
Vortex Break
 When the liquid outlet valve is open, a vortex breaker is normally installed to prevent vortex
formation.
 The formation of a vortex at the liquid outlet may cause gas to be withdrawn and entertained
with the existing liquid. This results in vapor loss, pump damage, and abnormal liquid level
readings. The bottom Baffle Plate Type Vortex Breaker has a diameter of 0.4D and is
positioned at L/2.
Mist Eliminator
 Mist elimination is the physical separation of liquids and gases. Mesh is typically made up of
0.011inch diameter wires that form a 4 to 6-inch-thick pad with a pressure drop of less than 1
inch of water.
Coalance
The rate of liquid phase separation can be increased by shortening the path through which the
droplets must rise or fall or by increasing their diameters. Both effects are obtained by forcing the
flow between parallel flat or crimped plates, tower packing, or a mass of packed fibers. The
disperse phase should wet the materials, which should be rough. Fine droplets will collide with the
surfaces and grow through the accretion of other droplets.
Design Steps:
 Calculation of Separation Factor.
 Calculate the system constant KH.
 Calculate the maximum vapor velocity.
 Calculate minimum flow area for vapors.
 Design volume based on design time to fill.
 Calculate the minimum cross-sectional area of the vessel.
65 | P a g e
 Calculate L/D.
 Pressure = P= 1.7 atm = 175 kPa

 Temperature = T = 40 ℃
 Liquid Phase Density = ρ = 826.76 kg/m3
 Vapor Phase Density = ρ = 20.43 kg/m3
 Mass Flow rate of Liquid Stream = M = 20639.27 kg/hr = 5.73 kg/s
 Mass Flow rate of Vapor Stream = M = 1289.50 kg/hr = 0.35 kg/s
Designing Calculations
Calculation of Separation Factor:

.
Separation Factor = M /M (ρ /ρ ) [16]
.
Separation Factor = 5.733131/0.358236(20.43016/826.768)
Separation Factor = 2.515745
Calculation of system constant KH
Kv for Separation Factor of 2.515 = (From Graph) [16]
Figure 4-5 System Constant
66 | P a g e
System Constant 𝑲𝑯 = 𝟎. 𝟎𝟔𝟓

Calculate Maximum Vapor Velocity:
V , . =K√ where K=K (Souder-Brown Equation) [18]
pl = 826.768 pv = 20.43016 K = 0.065

ᶟ ᶟ
826.768 − 20.43016
V = 0.065√
20.43016
= 0.408353 m/s
Calculate Minimum Flow Area of Vapors:
<A > = Q /V [16]

Volumetric Flow Rate:
For Liquid:
Liquid flow rate
Ql =
Density of liquid
.
Ql=
.
Ql = 0.006934 m /s
For Vapor:
Qv = [16]
.
Qv=
.
Qv = 0.01735 m /s
.
<A > = Q /V => <A > = => <A > = 0.04294 m
.
Design volume based on design Time to fill: [16]

Standard Design Time to fill = t= 3min – 5 min
Assumed Design Time to fill = t= 4 min
𝑉 =𝑄 ×𝑡
= 0.06934 × (4 × 60)
= 1.664253 𝑚
67 | P a g e
Minimum Cross-Sectional Area of the Vessel:
According to [16]
0.04294 m
<A > , =< A > /0.2 = = 0.2147 m
0.2
4 <A > , 4(0.2147)
Dmin = ^0.5 = ^0.5 = 0.522975 m = 20.58953 in
π π
Standard Phase separator internal Diameters are multiple of 6 in.

So, Next Smallest Multiple of 6
D = 24in = 0.609601
Calculating L/D:
V
L=
A
Area According to Standard Diameter:
D
A=π× = 0.2917 m
4
1.664253
L= = 5.705032 m
0.291717
4.3. Mechanical Design
Preliminary Data
 Material of construction is Stainless Steel 304
 Design Temperature = T = 40 °C
 Design Pressure = P = 110% of operating pressure
 Corrosion Allowance 2mm [11]
Calculations for Cylindrical Shell:
Pri
t= + Cc
SEj − 0.6P
68 | P a g e
Maximum Allowable Pressure= P= 1.2(P°)

P = 1.2(175 kPa) = 210 kPa
210 × 0.3
t= + 0.02 = 0.020557 m
114305(1) − 0.6(210)
Head Selection
Following table shows the criteria for head selection: [13]

Table 4-6 Head Selection
Pressure (bar) Head
P<15 Tori Spherical

P>15 Hemisphere
P>15 Ellipsoidal
Tori Spherical is selected because the pressure is below 15 bar

For Tori-Spherical Head:
According to [11]
0.88P×La 0.88×210×0.3
t= + Cc = 0.002 = 0.002593 m
SEj − 0.1P 94500(1) − 0.1×210
Specification Sheet for Flash Column:
Properties Values
Operating Temperature 40 °C
Operating Pressure 1.75 atm
Total Inlet Mass Flow Rate 21928 kg/hr
Total Gas Phase Mass Flow Rate 1289.65 kg/hr
Total Liquid Phase Mass Flow Rate 20639.27 kg/hr
Internal Diameter 0.6 m
Length 5.7 m
Head Type Tori Spherical
Shell Thickness 0.020557m
Head Thickness 0.027m
Material of Construction Stainless Steel 304
69 | P a g e
4.4. Distillation Column Design
Distillation is a thermal separation method for dividing mixtures of two or more substances into
individual fractions of the desired purity, based on differences in the volatility of the components,
which are actually related to the boiling points of these components, the application and removal
of heat. Note that the term distillation refers to a physical separation process or unit operation.
Distillation has undergone tremendous development due to the petrochemical industry and as such
is one of the most important technologies in the global energy supply system. All distillation
involves two steps: vaporization and condensation. [19]
Reason for using Distillation Column
Boiling Point Ratio: [20]

Propylene oxide is the light key and methanol is the heavy key
65℃
𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡 𝑟𝑎𝑡𝑖𝑜 =
35℃
𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡 𝑟𝑎𝑡𝑖𝑜 = 1.8 > 1.2
Types of Distillation
 Extractive distillation
 Flash distillation
 Steam distillation
 Vacuum distillation
 Azeotropic distillation
Extractive Distillation
Extractive distillation is defined as distillation in the presence of a miscible, high boiling, relatively
non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture.
Used for mixtures having a low value of relative volatility, nearing unity. Mixtures having a low
relative volatility cannot be separated by simple distillation because the volatility of both the
components in the mixture is nearly the same causing them to evaporate at nearly the same temperature
to a similar extent, whereby reducing the chances of separating either by condensation. [20]
70 | P a g e
Flash Distillation
In the flash evaporation process, a liquid is preheated and then subjected to a pressure lower than
its vapor pressure, causing it to boil or ignite. The seawater is first heated in the tubes and then
placed in a chamber with a lower vapor pressure than in the heating tubes and the liquid is
evaporated. The vapors separate from the warm liquid and the salts leave with the remaining water.
The process seems inefficient because the evaporation of a small amount causes a dramatic drop
in temperature. For example, when only 7.1% of the liquid evaporates, the temperature drops by
40 degrees, from 100 to 60 degrees Celsius. However, because the construction is so simple, it has
become a close competitor economically to multiple evaporation. This is especially true for larger
plants. [20]
Steam Distillation
Steam distillation is a special type of distillation (a separation process) for temperature sensitive
materials like natural aromatic compounds. In this method steam is guided over the plant material
containing the desired oils. It is also employed in the synthetic procedures of complex organic
compounds. [20]
Vacuum Distillation
Vacuum distillation is a method of distillation in which the pressure above the solution to be
distilled is reduced to less than one atmosphere (unit), causing the most volatile liquids (those with
the lowest boiling points) to evaporate. Vacuum distillation is used with or without heating the
solution; some distillation processes use both vacuum and heat. Vacuum distillation works on the
principle that boiling occurs when the vapor pressure of a liquid exceeds the ambient pressure (the
atmospheric pressure above it or the pressure in the still.) In standard thermal distillation, the vapor
pressure increases. During vacuum distillation, the ambient pressure is reduced. [20]
Azeotropic Distillation
Azeotropic distillation is any of a range of techniques used to break an azeotrope in distillation. A

common distillation with an azeotrope is the distillation of ethanol and water. Using normal
distillation techniques, ethanol can only be purified to approximately 95%. [20]
71 | P a g e
Choice Between Tray and Packed Column
 Wide ranges of liquid flow rates can be handled by plate columns without flooding.
 For very low liquid flows, packed columns are not appropriate.
 The packed column weighs more than the plate column for tall columns.
 When installing plates in columns with a diameter of less than 0.6 m, packing should always
be considered.
 Making cooling provisions for a plate column is simpler.
 A packed column will be less expensive for corrosive liquids than an equal plate column.
 Foaming liquids work well in packed columns.
 In a packed column as opposed to a plate column, the liquid holdup is noticeably lower.
 This is significant when it's necessary for safety reasons to have a minimal inventory of
poisonous or combustible liquids.
 Plate columns may be created with a higher rating.
Following table is summarizing the main difference between trays and packing: [11], [21], [22]
Trays vs Packing
Table 4-7 Trays vs Packing
Parameter Trays Packing
Flowrate High Low

Diameter Small Large
Side stream Possible Difficult
Foaming Can exists Lower
Efficiency Prediction Easy Difficult
For corrosive fluids Not used Used
Liquid holdup Higher Lower
Provision for cooling Easy Difficult
Trays are selected
72 | P a g e
Selection of Tray Type:
Types of trays are as follows;

 Valve tray
 Bubble cap tray
 Sieve tray
Following table is showing the comparison between different tray types: [15]
Table 4-8 Types of Trays
Factors Sieve Tray Valve tray Bubble-Cap tray
Capacity High High Low

Efficiency High High Moderate
Pressure drop Low Moderate High
Cost Low 1.2 times of Sieve tray 3 times of Sieve tray
Maintenance Low Moderate High
Sieve Tray has been selected because of the following reasons:

 High capacity
 Easier and cheaper to install
 Light in weight
 Low pressure drops
 Maintenance and cleaning are easy
 They can easily handle wide variations in flow-rate
Design Steps
 Specifying operating conditions

 Minimum number of stages.
 Minimum reflux.
 Actual reflux.
 Actual number of stages.
 Feed point.
 Distillation column Diameter calculations (Top and Bottom).
73 | P a g e
 Weir Length.
 Weeping.
 Pressure Drop.
 Down Comer liquid backup.
 Residence time.
 Entrainment (ψ).
 Perforated Area.
 L/D Ratio.
Design Conditions:
Table 4-9 Feed Conditions of Distillation Column
Feed Bottom Top
Dew Point = 83 oC Dew Point = 50.5 oC Dew Point = 89.81 oC

Bubble Point = 103.5 oC Bubble Point = 50.9 oC Bubble Point = 106 oC
Pressure = 175 kPa Pressure = 185 kPa Pressure = 165 kPa
Minimum Number of stages
The minimum number of stages is obtained from the Fenske relation: [11]
ln [(x /x ) (x /x ) ]
N =
ln (α / )
 x = fraction of Propylene oxide  x = fraction of methanol
 B = Bottom Product  D = Top Product
 α = Volatility
Putting Values in the above equation
N = 14.8
Reflux Ratio
Using Underwood Equations
αx ,
=1−q
α −∅
74 | P a g e
Where for saturated liquid q = 1 [23]

Putting Values
∅ = 1.99
αx ,
R +1= = 3.67
α −∅
R = 1.2(R ) = 4.407
Theoretical Number of Stages
.
N−N R−R
= 0.75 1 − => N = 31
N+1 R+1
N B x (x )
log = 0.206
N D x (x )
N + N = N = 31
N = 15.34 & N = 15.83
Feed plate is 16 from bottom
Vapor & Liquid Flowrate
Top Section:
L
R= => L =R×D
D
kmol
L = 319.6
hr
V =L + D = 338.8 kmol/hr
Bottom Section:
kmol kmol
𝐿 = 𝐿 + F = 925.4 𝑉 = 𝐿 − D = 392.13
hr hr
75 | P a g e
Diameter of Distillation Column
Top Section Diameter Calculation
925.4kmol
L =
hr
ρL = 860kg/m3 ρv = 1.5 kg/m3
L ρv
f = = 0.100
V ρ
Plate Spacing = 0.46m (Range 0.3-0.6) [15]

From Figure 11-34 R.K Sinnott [15]
.
б ρL − ρv . m
V =C = 1.85
20 ρv s
Operating Velocity at flooding = 0.70 V
m
Operating Velocity = V = 1.29
s
ṁ
Net Area(A ) = = 1.39m2
Operationg Velocity
A
Cross sectional Area(A ) = = 1.85m2
0.85
4A
D = = 1.44m
π
Bottom Section Diameter Calculations:
ṁ m
ρv = 3.470kg/m3 Vapour Volumetric flow = = 1.572
ρ sec
L ρ
F = = 0.06
V ρ
Plate Spacing = 0.46m (Range 0.3-0.6) [15]

From Figure 11-34 R.K Sinnott [15]
76 | P a g e
.
б ρL − ρv . m
V =C = 1.22
20 ρv s
Operating Velocity at flooding = 0.70 V
m
Operating Velocity = V = 0.855
s
ṁ
Net Area(A ) = = 1.83m2
Operationg Velocity
A
Cross sectional Area(A ) = = 2.16m2
0.85
4A
D = = 1.65m
π
Overall Tray Efficiency
Using O Connell’s Relation: [24]

.
E = 0.492 μ (α / )
𝐸 = 0.75 = 75 %
Actual Number of plates = 42 Feed Plate 21
Liquid Flow Arrangements
kmol
L = 925.4
hr
925.4kmol
Mols ∗ MW ∗ 26.17 m
L = = hr = 0.0078
3600 ∗ ρ 3600 sec/hr ∗ 860.5 kg/m s
From fig 11.28 [15]
Flow pattern= cross flow single pass
Height of Distillation Column
Height of Distillation Column = H = (N − 1)H + ∆H

H = (N − 1)H + 0.15H = (41 − 1)0.46 + 0.15H = 22.18m
77 | P a g e
Weir Dimensions:
Weir Height
A high weir will increase the plate efficiency but at the expense of a higher plate pressure drop.
For columns operating above atmospheric pressure, the weir heights will normally be between 40
mm and 90 mm (1.5 and 3.5 in.)
40 to 50 mm is recommended. [15]
So, 45 mm will be suitable.
Weir Length
A
X100 = 15
A
From Figure 11.31 [15]
l
= 0.81 => l = 0.81(D ) = 1.34 m
D
The weir length will normally be between 0.6 and 0.85 of the column diameters.
For this case it is 1.34/1.65 = 0.81 (Between) [15]
Weeping
kg
Maximum liquid flowrate = 6.73
s
Turn down ratio = 0.7
kg kg
Minimum liquid flowrate = 0.7(1.49 ) = 4.71
s s
L /
h = 750[ ]
ρ D
Where,
L = Maximum liquid flow rate. ρ =Density of liquid. l =Weir length.
/
kg
6.73
Maximum h = 750 s = 24.3 mm liquid
kg
860 × 1.11 m
m
78 | P a g e
/
4.71kg
Minimum h = 750 s = 19.2mm liquid
kg
860 × 1.11 m
m
Hw=50 h +h = 69.2 mm liquid
From figure 11-30 [15] K2 = 30.6
As,
K2 − 0.90(25.4 − d )
u =
(ρ ) 0.5
Where, u = Minimum design Vapour velocity
d = Dia of hole ( 5mm assumption )
So, u = 9.77
Actual Minimum Vapor Velocity
Minimum vapour rate

Actual minimum vapour velocity =
Area of hole
Trail – 1:
Area of hole = 5% of Active Area = 0.07m
SO, v = 14.01 > u
Pressure Drop
uh max ρV
h = 51
C ρL
Bottom Volumertric flow rate m
u = = 24.05
Area of hole s
Plate thicknes
For =1
Hole Diameter
And × 100 = 5
From figure 11-34 [15], we get

C0= 0.82
h = 2.7 mm liquid.
Residual Head:
79 | P a g e
12.5 × 10 12.5 × 10
h = = = 14.5 mm liquid
ρL 850
Total Pressure Drop:
h = h + (h + h ) + h = 86.4 mm liquid
Plate pressure Drop
kg
∆P = 9.81 × 10 h ρ = 9.81 × 10 × 86.4 × 860 = 0. 729kPa
m
Down-Comer Liquid Backup
h = h − 10 = 40 mm liquid
Area Under Apron, A =l ×h = 0.21m < A
So, we can use equation 11.60 [15]
h = 166 = 0.0052 mm liquid
h = (h + h )+h +h = 155.6 mm liquid

1
h < (Plate Spacing + Weir length) < 0.90m
2
Where hdc is head loss in down comer
Residence Time
Down comer Area × h × ρ

Residence time = = 7.67 s
L
Entrainment
u minimum vapour flowrate m

Entrainment = = = 1.55
u A s
%age flooding:
Entrainment
%ageflooding = × 100 = 48%
u
As, f = 0.100
From Figure 11.29 [15], Entrainment = ψ = 0.009 < 0.1
80 | P a g e
Perforated Area
Weir length l
= = 0.927
COlumn dia D
From figure 11.34 [15]
θ = 110°
So,
Angle subtended by the edge of plateθ = 180° − 110° = 70°
Unperforated edge strip length and Calming zone width = 50mm
70°
Mean length, unperforated edge strip = (1.28 − 55 × 10 )π × = 1.49 m
180°
So, Area of unperforated edge strip = Length ∗ Width = 0.082m
Mean length, Calming zone = Weir length + Width of Calming zone
Mean length, Calming zone = 1. 399m
Area of Calming zone = 0.153 m
Total Area of Perforation
= Active Area − Area of unperforated edge strip − Area of calming zone
Total Area of Perforation = A = 1.04 m
A
= 0.0086
A
Number of Holes
From Figure 11.33 [15]

l
= 3.2
d
π π
Area of one hole = D = (5 × 10 ) m = 1.964 × 10 m
4 4
A
Number of holes = = 458.598 holes.
Area of one hole
Length/Diameter (L/D) Ratio
L Lenght
= = 13.37 < 20
D Diameter
81 | P a g e
Specification Sheet of Distillation Column
Specification sheet
Identification
Item Distillation
Item no. D-101
No. required 1
Tray type Sieve
Operation Continuous
Function
Separation of Propylene Oxide
Material Handled
Parameters Feed Top Bottom
Quantity 18283.29kg/hr 72.60kmol/hr 533.46kmol/hr
Temperature 83℃ 50.55℃ 89.91℃
Design Data
No. of trays 42
Pressure drop 0.729 kPa
Height of column 22.18 m
Diameter of column 1.65m
Reflux ratio 4.6
Tray spacing 0.46 m
Material of construction Stainless Steel
4.5. Heat Exchanger Design
Heat exchanger is one of the most commonly used process equipment in industry and research.
Function of a heat exchanger is to transfer energy; this transfer of energy may occur to a single
fluid (as in the case of a boiler where heat is transferred to water) or between two fluids that are at
different temperatures (as in the case of an automobile radiator where heat is transferred from hot
water to air). In some cases, there are more than two streams of fluid exchanging heat in a heat
exchanger. Heat exchangers of several designs in a variety of sizes varying from ‘miniature’ to
‘huge’ (with heat transfer areas of the order of 5000 to 10,000 sq. meters) have been developed
over the years. [25]
For this process the aim of the heat exchanger design is to heat the solvent that will be used to
carry out the reaction in the reactor.
82 | P a g e
Design of Key Exchanger Type
Since there are many alternative designs that would meet a specific heat duty, it is necessary to
optimize the design. The process by which the design engineer moves from one design to a more
satisfactory one and its relationship to the total design process are shown in Figure below
Figure 4-6 Structure for the Process of Heat Exchanger Design Logic
The critical feature of the design process is the design modification step. If it is done by hand, the
design modification is largely intuitive and depends on the design engineer's experience and
insight. However, if the design process is carried out with a fully integrated computer program,
the success of the process is heavily dependent on the skill and care with which the design logic
has been constructed. Since it is impossible to check all these possibilities, great care and
conservatism must be exercised in spelling out these decision points. [11]
Types of Heat Exchanger
Following table is showing different types of heat exchanger with their features and limitations: [11]
83 | P a g e
Table 4-10 Heat Exchanger Types with Their Features and Limitations
Exchanger type Features and limitations
Double Pipe Heat Exchanger Capacity Small scale
Expensive Less
H.T area Maximum
Fluid viscosity Both high/low

Shell and Tube Heat Capacity Large scale
Exchanger
Expensive Less
H.T area Maximum
Fluid viscosity Both

Gasket and welded plate Capacity Small scale
exchanger
Expensive Much
H.T area Maximum
Fluid viscosity Viscous

Compact heat exchanger Capacity Large scale
Expensive Much
H.T area Maximum
Fluid viscosity Gas-gas
Preliminary Selection:
Q = UA∆T
 Q = 104.63 kW  U = 460 W/m2.K [11]
 ∆T = log mean temperature difference
∆T − ∆T
∆T =
∆T
ln
∆T
84 | P a g e
 T , = 100 ℃  T , = 100 ℃
 T , = 25 ℃  T , = 40 ℃
 ∆T = 60 ℃  ∆T = 75 ℃
By putting values in the equation ∆T = 67 ℃
And A = 3.4 𝑚
According to following table both heat exchanger can be used. But the double pipe heat exchanger
is probably the best choice for this small high-pressure heat transfer application since the modular
construction of this type of exchanger provides a significant cost advantage. [11]
Table 4-11 Selection Between Double Pipe and Shell & tube Heat Exchanger
Exchanger Type Temperature range °C Area range, 𝑚𝟐

Double pipe -100 to 600 0.25 to 20
Shell and tube -200 to 600 3 to 1000
Fluid Placement
 There are a number of practical guidelines which can lead to the optimum design of a given
heat exchanger. Remembering that the primary duty is to perform its thermal duty with the
lowest cost yet provide excellent in-service reliability, the selection of fluid stream
allocations should be of primary concern to the designer.
 There are many trade-offs in fluid allocation in heat transfer coefficients, available pressure
drops, fouling tendencies and operating pressure. The higher-pressure fluid normally flows
through the tube side. With their small diameter and nominal wall thicknesses, they are
easily able to accept high pressures and avoid more expensive, larger diameter components
to be designed for high pressure.
 If it is necessary to put the higher-pressure stream in the shell, it should be placed in a
smaller diameter and longer shell. Place corrosive fluids in the inner pipe, other items being
equal. Corrosion is resisted by using special alloys and it is much less expensive than using
85 | P a g e
special alloy annuals materials. Other inner pipe side materials can be clad with corrosion
resistant materials or epoxy coated flow the higher fouling fluids through the inner pipe.
Design Steps
 The main steps of design are as follows

 Calculate ΔT1 and ΔT2 from temperature profile.
 Calculate LMTD.
Annulus:
 Calculate equivalent diameter

 Calculate flow area a
 Mass velocity, G
 Obtain μ and Jh
 Calculate ho
 Calculate Overall coefficient Uc
 Calculate Ud
 Calculate area from Q
Pressure Drop Calculation:
Inner Pipe:
 Calculate Reynold number, Re

 Calculate ΔFp
Annulus:
 Calculate Equivalent diameter De

 Calculate ΔFp
86 | P a g e
Calculation of LMTD
Steam
100℃ 100℃
40℃
25℃
Figure 4-7 LMTD for Heat Exchanger
 T , = 100 ℃  T , = 100 ℃
 T , = 25 ℃  T , = 40 ℃
 ∆T = 60 ℃  ∆T = 75 ℃
By putting values in the equation ∆T = 67 ℃
Calculations:
( ℃ ℃)
Avg temperature = = 32.5 ℃ = 90℉
From fig 2 [26], we take value of Cp, Cp = 0.64

Heat duty Q = 104.06kW = 104060 W
For steam (From Saturated Steam Table D.Q Kern) [26]
⅄ = 2260 kj/kg
Q=m⅄
m= = 104060.41𝑊/2260𝑘𝑗/𝑘𝑔 = 104060.41j/s / 2260000j/kg = 0.0463 kg/s
⅄
hi= 8517.45 w/ 𝑚2. ◦C (Fixed)

flowrate of Methanol = 9931 kg/hr = 2.7586 kg/s
Assume pipe dimension 3x2 IPS [26]
Also, from table 3.6 [26], the flow area of pipe is greater
87 | P a g e
Table 4-12 Dimensions for Double Pipe Heat Exchanger
3 (Schedule 40) 2 (Schedule 40)

OD = 0.0889m OD = 0.0604m
ID = 0.0779m ID = 0.0525m
D1 = 0.0604m D2 = 0.0779m
( ₂² ₁²)
a= = 𝜋 [(0.0779)²- (0.0604)²]/4 = 𝜋 [0.0060 – 0,0036]/4
= 0.007536/4 = 0.00187 𝑚2
G=
= 2.7586kg/s / 0.00187 𝑚² = 1455.3371 kg/ m².s
μ from fig 14 [26], μ = 0.0005 kg/m.s
Using formula
( . )
Re=
( ₂² ₁²)
De = = (0.0779)²- (0.0604)²/ 0.0604 = 0.0060 – 0.0036/0.0604 = 0.0399 m
Putting values in formula, we get

Re = (0.0397m)(1455.3367 kg/𝑚².s / 0.0005 kg/m.s = 116301.07
Jh from figure 24 [26], Jh = 40
From table 4, k=0.2144 W/m. ◦C
As, ho = (40) (0.2144/0.0399) (0.64 x 0.0005 /0.2144)⅓
ho = 395.2064 W/ 𝑚². ◦C
hi x ho
𝑈 =
hi + ho
Uc = (8517.45) (395.2064) / 8517.45 + 395.2064 = 377.6821 W/ 𝑚². ◦C
1/ U = 1/U + R
Required Rd is 0.0003
Putting, values we get
1 1
= + 0.0003 = 0.00596
U 252.298
Ud = 333.3391 W/ 𝑚². ◦C
88 | P a g e
Q = Ud A Δ Tlm
𝑄
𝐴=
Ud Δ T lm
A = 104060 W/( 333.3392 W/𝑚².◦C )(67◦C ) = 3.6896 𝑚²
According to Table 11 [26], the external surface area = 0.1895m
= 3.6896 𝑚²/0.1895 m
= 24.3787m linear length
Number of Pins required = 2
= 24.3787 x 0.1895 = 4.6201 𝑚²
Q =𝑈 𝐴 𝛥 𝑇 𝑙𝑚 , Ud =
Ud = 104060 W/( 5.6 𝑚²)(67 ◦C) = 266.2012 W/𝑚². ◦C

Ud – Uc
𝑅 =
Ud x Uc
Rd = 355 – 252/ (355)(252)
Rd = 0.0011
Pressure Drop calculation
Annulus Calculation
De = 𝐷₂ − 𝐷₁ = 0.079 – 0.0604 = 0.0175m

Re = (0.0175m) (1480.1871kg/ 𝑚².s) / (1.8013 kg/m.s) = 50740.548
f = 0.0035 + 0.264/ DG/U)0.42 = 0.0035 + 0.264/95.54 = 0.003505
S = 0.79 from table 6 [26], ρ = 49.375 lb/ft³
²
∆𝐹 = = 4(0.00626) (1094892.75) ² = 11.0270 ft
²
Δ Fa = 4(0.00626) (1094892.75)² = 11.0270 ft

V = Go/3600f = 1094892.75/3600(49.4) = 1480.18 kg/ 𝑚².s / 177.840 kg/m³ = 6.0280 m/s
Δ Fl = 8(𝑉²/2𝑔)
Δ Pa = 36.5435 KPa
That is < 69KPa [26]
89 | P a g e
Inner Pipe Calculation
Re = 152398.7
f = 0.0035 + (0.264/152398.7)^0.42 = 0.0035 + (0.264/135.2631) = 0.0052
S= 0.79, Density=0.79x62.4 = 49.3
²
∆𝐹 = = 4(0.0052) (1071485)2(80)/2 x 4.18 x 108 x (49.3)² x 0.075
²
Δ Fv = 2.07 x 1012 / 1.52 x 1011 Δ Fa = 13.6

Δ P = 13.6 x 49.3/ 144 = 39.0932 kPa, That is < 69 kPa [26]
90 | P a g e
4.6. Simulation of Plant
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Procedure:
 Start Aspen HYSYS
 Select New to create a new simulation. [27]
 Go to component list and create a component list and click add to add the component.
Figure 4-8 Adding of Components in Aspen HYSYS
 Select a property package.
Figure 4-9 Adding Fluid Package in Aspen HYSYS
92 | P a g e
These both Fluid packages can be used for this case.

 Now create a reaction set (Epoxidation). Go into reactions, click on add, to add reactions.
Figure 4-10 Adding Reaction Set in Aspen HYSYS
 For the conversion reaction click on the conversion reaction

 Now double click on the reactions to add the component, stoichiometric coefficients and
conversion of the reaction.
Figure 4-11 Adding Reactions in Aspen HYSYS

93 | P a g e
Figure 4-12 Adding Coefficients of Reaction 1
Figure 4-13 Adding Coefficients of Reaction 2
 Now click on the add to FP to add fluid package to the set.

 Enter the simulation environment. Click the Simulation button in the bottom left of the
screen.
 Specify all feed composition, temperature, pressure. [27]
 Add all the equipment from model pallet and perform all the simulation on each
equipment.
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Calculations
Worksheet of Pump (P-101)
Figure 4-14 Worksheet of Pump (P-101)

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Worksheet of Heat Exchanger (HX-101)
Figure 4-17 Worksheet of Heat Exchanger (HX-101)
96 | P a g e
97 | P a g e
Worksheet of Mixture (MIX-101)
Figure 4-20 Worksheet of Mixer (MIX-101)
Worksheet of Reactor (R-101)
Figure 4-21 Worksheet of Reactor (R-101)

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Worksheet of Valve (VLV-101)
Figure 4-22 Worksheet of Valve (VLV-101)
Worksheet of Flash Column (FC-101)
Figure 4-23 Worksheet of Flash Column (FC-101)

99 | P a g e
Worksheet of Stripper (St-101)
Figure 4-24 Worksheet of Stripper (St-101)
Worksheet of Distillation Column (DC-101)
Figure 4-25 Worksheet of Distillation Column (DC-101)

100 | P a g e
Worksheet of Distillation Column (DC-102)
Figure 4-26 Worksheet of Distillation Column (DC-102)
References
[1] A. K. Coker, Modeling of chemical kinetics and reactor design. Gulf Professional
Publishing, 2001.
[2] S. B. Thakore and B. I. Bhatt, Introduction to process engineering and design. McGraw-
Hill Education, 2007.
[3] P. H. Groggins and P. H. Groggins, "Unit processes in organic synthesis," 1958.
[4] H. S. Fogler and S. H. Fogler, Elements of chemical reaction engineering. Pearson
Educacion, 1999.
[5] H. Silla, Chemical process engineering: design and economics. CRC Press, 2003.
101 | P a g e
[7] A. Sulimov, S. Danov, A. Ovcharova, A. Ovcharov, and V. Flid, "Kinetics of propylene

epoxidation with hydrogen peroxide catalyzed by extruded titanium silicalite in methanol,"
Kinetics and Catalysis, vol. 57, no. 4, pp. 466-473, 2016.
[8] O. Levenspiel, Chemical reaction engineering. John wiley & sons, 1998.
[9] Napoli, Industrial & Engineering Chemistry Research. . pp. 6274-6287, 2014.
[10] P. Mehrani, Particles and Multiphase Systems. Ottawa, 2016.
[11] M. S. Peters, K. D. Timmerhaus, and R. E. West, Plant design and economics for chemical
engineers. McGraw-Hill New York, 2003.
[12] techsteel.net/tube-sizing-chart. Tube Sizing Chart, 2022.
[13] R. Sinnott, "Coulson & Richardson’s chemical engineering, vol. 6," Chemical engineering
design, vol. 4, 2005.
[14] C. L. Yaws and C. Gabbula, Yaws" Handbook of thermodynamic and physical properties
of chemical compounds. Knovel, 2003.
[15] G. TOWLER and R. SINNOTT, "CHEMICAL ENGINEERING DESIGN Principles,
Practice and Economics of Plant and Process Design," 2008.
[16] R. B. Carl, "Rules of thumb for chemical engineers," ed: USA: Gulf Publishing Company,
1998.
[17] J. R. Couper, W. R. Penney, J. R. Fair, and S. M. Walas, Chemical process equipment:
selection and design. Gulf professional publishing, 2005.
[18] M. Souders and G. G. Brown, "Design of fractionating columns I. Entrainment and
capacity," Industrial & Engineering Chemistry, vol. 26, no. 1, pp. 98-103, 1934.
[19] A. A. Kiss, Advanced distillation technologies: design, control and applications. John
Wiley & Sons, 2013.
[20] B. K. Dutta, "Mass Transfer and separation processes," Eastern economy edition, PHI
learning private ltd, New Delhi, 2009.
[21] B. J. McCoy, "CHEMICAL ENGINEERING: Vol. 2. Particle Technology and Separation
Processes, by JM Coulson, JF Richardson, JR Backhurst, and JH Harker," Chemical
Engineering Education, vol. 27, no. 3, pp. 183-199, 1993.
[22] R. W. Rousseau, Handbook of separation process technology. John Wiley & Sons, 1987.
102 | P a g e
[23] W. L. Mc Cabe, J. C. Smith, and P. Harriott, Unit operation of chemical engineering.

McGraw-Hill, 2018.
[24] D. W. Green and M. Z. Southard, Perry's chemical engineers' handbook. McGraw-Hill
Education, 2019.
[25] M. Thirumaleshwar, Fundamentals of heat and mass transfer. Pearson Education India,
2006.
[26] D. Q. Kern and D. Q. Kern, Process heat transfer. McGraw-Hill New York, 1950.
[27] J. Haydary, Chemical process design and simulation: Aspen Plus and Aspen Hysys
applications. John Wiley & Sons, 2019
103 | P a g e
CHAPTER 5: ENVIRONMENTAL SAFETY AND CONTROL STUDY
5.1. Instrumentation and Control
Instrumentation
Instruments are provided to monitor the key process variables during plant operation. They may
be incorporated in automatic control loops or used for manual monitoring of process operation. In
most modern plants, the instruments will be connected to a computer control and data logging
system. Instruments monitoring critical process variables will be fitted with automatic alarms to
alert the operators to critical and hazardous situations. [1]
Control
A chemical plant is an arrangement of processing units (reactors, heat exchangers, pumps,

distillation columns, absorbers, evaporators, tanks, etc.), integrated with one another in a
systematic and rational manner. The plant's overall objective is to convert certain raw materials
(input feedstock) into desired products using available sources of energy, in the most economical
way. During its operation, a chemical plant must satisfy several requirements imposed by its
designers and the general technical, economic, and social conditions in the presence of ever-
changing external influences (disturbances). Among such requirements are the following: [2]
 Safety
 Production specifications
 Environmental regulations
 Operational constraints
 Economics
All the requirements listed above dictate the need for continuous monitoring of the operation of a
chemical plant and external intervention (control) to guarantee the satisfaction of the operational
objectives. This is accomplished through a rational arrangement of equipment (measuring devices,
valves, controllers, computers) and human intervention (plant designers, plant operators), which
together constitute the control system. [2]
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Instrumentation and Control Objectives
The primary objectives of the designer when specifying instrumentation and control schemes
are: [1]
1. Safe plant operation
 To keep the process variables within known safe operating limits.
 To detect dangerous situations as they develop and to provide alarms and automatic shut-
down systems.
 To provide interlocks and alarms to prevent dangerous operating procedures.
2. Production rate
 To achieve the design product output.
3. Product quality
 To maintain the product composition within the specified quality standards.
4. Cost
 To operate at the lowest production cost, commensurate with the other objectives.
5. Stability
 To maintain steady, automatic plant operation with minimal operator intervention.
Variables in a Chemical Process
The variables (flow rates, temperatures, pressures, concentrations, etc.) associated with a chemical
process are divided into two groups: [2]
1. Input variables, which denote the effect of the surroundings on the chemical process
 Manipulated (or adjustable) variables, if their values can be adjusted freely by the human
operator or a control mechanism
 Disturbances, if their values are not the result of adjustment by an operator or a control
system.
2. Output variables, which denote the effect of the process on the surroundings.
 Measured output variables, if their values are known by directly measuring them
 Unmeasured output variables, if they are not or cannot be measured directly
105 | P a g e
Design Elements of a Control System
Following are the design elements of any control system: [2]

 Define control objectives
 Select measurements
 Select manipulated variables
 Select the control configuration
 Design the controller
Components of the Control System
Following are the components of the control system: [2]

1. The chemical process: It represents the material equipment together with the physical or
chemical operations that occur there.
2. The measuring instruments or sensors: Such instruments are used to measure the
disturbances, the controlled output variables, or secondary output variables, and are the
main sources of information about what is going on in the process.
3. Transducers: Many measurements cannot be used for control until they are converted to
physical quantities (such as electric voltage or current, or a pneumatic signal, i.e.,
compressed air or liquid) which can be transmitted easily. Transducers are used for that
purpose.
4. Transmission lines: These are used to carry the measurement signal from the measuring
device to the controller.
5. The controller: This is the hardware element that has "intelligence." It receives the
information from the measuring devices and decides what action should be taken.
6. The final control element: This is the hardware element that implements in real life the
decision taken by the controller.
7. Recording elements: These are used to provide a visual demonstration of how a chemical
process behaves.
Types of Control Configuration
There are three main types of control configurations [2]
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 Feedback Control: Such a control employs changes into the system to bring back the
process back into the desired condition after disturbances have been felt and experienced
by the system.
 Feed-forward Control: Considered to be the exact opposite of Feedback, as the
configuration tries to estimate the effect of the disturbances on the system and adjusts
accordingly before the said disturbances affect the system.
 Inferential Control: Uses a set of secondary measurements to give us the value of the
desired parameter. It is basically a sub-class of the above two configurations, nevertheless,
its uniqueness allowed itself to exist as a separate category.
Types of Controller
Three main types of controllers are usually used: [2]

 Proportional Controller (P-Controller): The controller whose output is proportional to
the error.
 Proportional-Integral Controller (PI-Controller): Output resets after a specific time, as
an addition to the already present output, including the action of P-Controllers.
 Proportional-Integral-Derivative Controller (PID-Controller): Estimates future error
and acts accordingly and functions with both PI and P controller actions as well
5.2. Distillation Column Control System
Distillation Control Objectives
The starring point of any design project is a definition of objectives. For distillation there are many
possible approaches, but the one chosen here is one that have found broadly useful in virtually all
kinds of processes. It has three main facets: [3]
1. Material-balance control
 The column control system must cause the average sum of the product streams to be exactly
equal to the average feed rate.
 The resulting adjustments in process flows must be smooth and gradual to avoid upsetting
either the column or downstream process equipment fed by the column.
107 | P a g e
 Column holdup and overhead and bottoms inventories should be maintained between
maximum and minimum limits.
2. Product quality control
 Maintain the concentration of one component in either the overhead or bottoms at a
specified value.
 Maintain the composition at the other end of the column as close as possible to a desired
composition.
3. Satisfaction of constraints
 The column shall not flood.
 Column pressure drop should be high enough to maintain effective column operation, that
is, to prevent serious weeping or dumping.
Control on Distillation Column
Temperature Control
Table 5-1 Temperature Control of Distillation Column
Process Distillation
Control Scheme Feedback Control System
Controller type PID controller
Disturbance Feed Temperature
Controlled Variable Temperature (at bottom)
Manipulating Variable Stream flow rate
Measuring Element Thermocouple
Final Control Element Valve
Level Control
Table 5-2 Level Control of Distillation Column
Disturbance Feed Flow rate
Controlled Variable Liquid level (Bottom + Top)
Manipulating Variable Bottom product flow rate
Measuring Element Liquid head pressure devices
Final Control Element Valve (bottom product)
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Composition Control
Table 5-3 Composition Control of Distillation Column
Disturbance Composition at the feed
Controlled Variable Composition of Distillate
Manipulating Variable Reflux ratio
Measuring Element Composition analyzer
Final Control Element Reflux valve
Piping and Instrumentation Diagram of Distillation Column
Figure 5-1 Distillation Column P&ID Diagram
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5.3. HAZOP Study
The hazard and operability study, commonly referred to as the HAZOP study, is a systematic
technique for identifying all plant or equipment hazards and operability problems. In this
technique, each segment (pipeline, piece of equipment, instrument, etc.) is carefully examined, and
all possible deviations from normal operating conditions are identified. [4]
The HAZOP analysis utilizes key guide words and system diagrams (design representations) to
identify system hazards. Adjectives (guide words) such as more, no, less, and so forth are
combined with process/system conditions such as speed, flow, pressure, and so on in the hazard
identification process. HAZOP analysis looks for hazards resulting from identified potential
deviations in design operational intent. [5]
Purpose of HAZOP Study
The purpose of HAZOP analysis is to identify the potential for system deviations from intended
operational intent through the unique use of key guide words. The potential system deviations then
lead to possible system hazards. [5]
Advantages of HAZOP
 In the design of new plants, designers sometimes overlook few issues related to safety in
the beginning. This may result in few errors. HAZOP highlights these errors. HAZOP is
an opportunity to correct these errors before such changes become too expensive or
impossible. [6]
 HAZOP is a preferred tool of risk evaluation because of few reasons: (i) easy to learn; (ii)
can be easily adapted to almost all operations in the process industries; (iii) is a common
method in contamination problems rather than chemical exposure or explosions; and (iv)
requires no special level of academic qualification to perform HAZOP studies.
 HAZOP studies examine the full description of the process thoroughly.
 HAZOP penetrates into greater depth of risk analysis of any process plant. HAZOP, applied
on the same type of plant, repeatedly improves safety, which is quite important. Potential
failures that were not noticed in the earlier studies can be easily highlighted using HAZOP.
110 | P a g e
HAZOP Flowchart
HAZOP studies are not carried out on the whole layout of the process plant but only on the chosen
segments of the plant. Usually, such segments are identified through preliminary studies. [6]
5.4. HAZOP Study of Heat Exchanger

Table 5-4 HAZOP Study of Heat Exchanger
Guide Word Deviation Causes Consequences Action
Less Less flow of Pipe blockage Temperature of Low temp Alarm

steam process fluid
decreases
More More flow of Failure of valve Temperature of High temp
steam process fluid Alarm
increases
More of More pressure Failure of fluid Bursting of inner Install
on inner pipe pipe prevention alarm
Contamination Contamination Leakage of inner Contamination Proper
of process fluid pipe of process fluid maintenance
line
corrosion Corrosion of Impurities Less heat Proper
inner pipe transfer and maintenance
cracks of inner
pipe
5.5. EIA Study
Introduction to Environmental Impact Assessment
The Environmental Impact Assessment (EIA) report is an assessment of the positive or negative
impacts that the proposed project may have on the environment, which includes environmental,
social and economic factors. [7]
The purpose of the survey is to ensure that decision makers consider the following environmental
impacts when deciding whether to proceed with a project or not. The International Association for
Impact Assessment (IAIA) defines environmental impact assessments as "the process of
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identifying, predicting, evaluating and mitigating the biophysical, social and other relevant effects
of development proposals before major decisions and commitments have been made." [7]
Importance of EIA
The EIA today is being used as a decision-making tool rather than a decision-making tool. It aims
to identify, predict, evaluate and mitigate the biophysical, social and other relevant effects of
development proposals before major decisions and commitments are made. [8]
The EIA covers a number of factors that must be considered before making decisions. It makes it
easy to see
 The most environmentally suitable option at an early stage
 Alternative processes
Contents of EIA
 A description of the project

 Description of significant effects
 Mitigating Measure
Proposed Plant Location
The geographic location of a final plant can have a strong influence on the success of an industrial
venture. The proposed location selected for the production of 100 MT/day of Propylene oxide is
Gwadar, Baluchistan. Primarily, this is selected because minimum cost of production and
distribution can be obtained by import and export of reactants and product respectively while
considering other factors (Energy availability, Climate, Water supply, Waste disposal, Labor
supply, Taxation and legal restrictions, Site characteristics, fire protection, Community factors) as
well.
Physical Baseline
The physical baselines include land, topography, climate, Area, Natural sources etc.
Introduction
Gwadar is Pakistan's largest coastal region and is located on the southern and western frontiers.
The district was formed in 1977 with the division of the Mekran district into three counties of
112 | P a g e
Kech, Panjgur and Gwadar. It is located between 25o - 01 'and 25o - 45' latitude north and from
61o - 37 'to 65o - 15' east. The region is bordered to the north by Kech and to Awaran, to the east
by Lasbela, to the south by the Arabian Sea, and to the west by Iran. [9]
Topography
Gwadar is a long coastline region south of the Mekran Coast Range. The region's coastline covers
600 kilometers covering 78 percent of the province's coast and 55 percent of the entire coast of
Pakistan. The central coast is low, with high white sand dunes, grassy sand dunes or in some places
a very low sand dune line with mangrove swamps behind it. Near the sea, rivers, which are very
dry, form rivers of salt water. [9]
Area
DCR 1981, The 1997 District Profile of Gwadar and Situation Analysis Study of Gwadar District
(unpublished) conducted in 2005 reported that the total area of the region was 15,216 square
kilometers. According to DCR 1998, the area of Gwadar district is 12,637 square kilometers. [9]
Climate
With a dry, hot climate, Gwadar is located in a ‘warm summer and cool winter. The effect of the
sea is to keep the summer temperatures low and the winter temperatures higher than the hinterland
areas. Winter lasts three months from December to February and is pleasant without occasional
cold or short. According to weather data recorded in Pasni, May and June are the hottest months
with a maximum temperature of about 35oC and December-January are the coldest months with a
minimum temperature of about 13oC. The climate is dry and rainy. Most of the rainfall occurs
between December and February with an average annual rainfall of 20 mm. For the remaining nine
months of the year, the highest rainfall is 12 mm in August. [9]
Natural Resources
The region is rich in natural resources. The largest source of coastline and ocean that provides
livelihoods for most people. Fish are an important natural resource from the ocean. Salt is extracted
from seawater in the region. Wind is another important unused resource that can be used to
generate electricity through wind turbines along the coast as sufficient wind power is available in
Gwadar. Pakistan Petroleum Limited has obtained an oil and gas exploration permit from the GoP
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for two overseas exploration blocks. Forest sources are small, with the exception of two large
mangrove forest areas along the coast. Livestock is raised in rural areas in small quantities. There
are no large livestock farms in the region. Agriculture has nothing but flooded areas and a few
water pipes. [9]
Environment
Gwadar faces a growing number of environmental problems. Being a coastal region where the sea
provides livelihood for many people and puts Gwadar in danger. The coast is one of the busiest
shipping lanes in the world with nearly 11,000 ships weighing 12,000 tons and 2,500 tanks
carrying 33 million tons of oil annually. Oil pollution already appears to be a problem along the
coast of Gwadar and Pasni. Reports indicate that the sea level is rising steadily but steadily at
various times in various parts of the world due to global warming. . In recent years, there has been
an increase in traffic congestion in the region, especially in Gwadar Town. Emerging greenhouse
gas emissions pollute the air in densely populated urban areas. [9]
Economy
Significant changes in the economic activities of the region have already taken place. Construction
has emerged as the second largest economic activity after fishing. The population of Gwadar is
growing rapidly with relocation to cater for emerging job opportunities in the construction
industry. These conditions are indicative of changes in the economy, economic activity and
employment patterns. [9]
Environment Impact During the Construction of Plant
It is guaranteed that the construction industry can have a significant impact on the environment,
but the actual level of sector pollution is made clear by numbers. The construction is believed to
be responsible for air pollution, more water pollution cases than any other industry, and thousands
of complaints from noise every year. [10]
Environmental Impact of Construction: Air Pollution

Construction has a significant impact compared to air pollution, and the causes of air pollution can
include ground cleaning, diesel engine operation, demolition, burning, and toxic use. As anyone
who has ever worked on a site will know, construction can produce a lot of dust, whether with
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building materials such as cement and stone, local vehicles, or demolition work and there is a risk
that this dust could affect local areas. [10]
Mitigation Measures
 Limit Fuel Usage [11]

 Minimize haul distances
 Reduce vehicle idling time
 Use greener, alternative fuel sources
 Use hybrid equipment
Environmental Impact of Construction: Water Pollution
In construction, water pollution can occur when water containing contaminants comes out of an
area flowing into the surrounding water. Dangers here can be as simple as muddy water being
dumped in a river or a nearby stream, known as soil pollution, or invisible problems such as surface
runoff containing harmful chemicals such as paint, solvents, and diesel. Meanwhile, chemical
pollutants can sink in groundwater, affecting drinking water. [11]
Mitigation Measures
 View and improve your management and disposal of domain waste. Make sure all waste
is handled properly to prevent the spread of contamination.
 Keep items such as sand or cement safe. Equipment should be stored where there is no risk
of washing in water or drains.
 Close all drains to prevent waste from entering the water.
 Keep the road and footpath clean at all times. This will prevent mud and other contaminants
from entering any body of water.
 Thoroughly collect and clean the contaminated water you produce
Environmental Impact of Construction: Noise Pollution
Noise may not be the first thing to remember when it comes to the effects of pollution, but the
problem can be very serious. Obviously, construction sites can be noisy, due to the heavy use of
heavy machinery, vehicles and equipment, but also shouting and loud radios. High levels of
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background noise carry the risk of affecting local residents and construction workers but can also
have an impact on local wildlife. [12]
Mitigation Measures
 Use quiet electrical tools and equipment to control noise pollution. Where possible, use
modern materials that are specially designed to produce minimal noise.
 Schedule work for leisure time rather than for residents to sleep. For example, between 8
and 6pm during the week. You can also inform local residents of working hours and keep
them up-to-date on the project.
 Install acoustic barriers (noise) to control noise pollution levels.
 Ensure that industries and equipment are maintained and functioning properly.
 Turn off the plant when not in use.
 Make sure staff wear appropriate PPE if necessary to reduce the risk of hearing loss due to
loud noise.
Environmental Impacts and Mitigation Associated with Operational Activities:

The Proposed Project
The proposed project is the production of 100 Metric ton/day of Propylene Oxide
The major equipment’s in the proposed plant include:
 Heat Exchangers
 Pumps
 Reactor
 Flash Column
 Stripper
 Distillation Columns
EIA of Propylene Oxide
Propylene oxide affects a person's health primarily through smell and skin contact. Inhalation of
PO leads to various health problems such as respiratory irritation, damage to the central nervous
system, and possibly pneumonia. It is important to note that human exposure to the environment
is estimated at 3.9 µg / kg / day in the local environment while 3 ng / kg / day in the regional
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environment. Exposure to PO skin occurs at the production site where operators are at risk of
contact with contaminated areas or direct contact with the skin. However, most dermal exposure
is less than 1 ppm as processing occurs in closed systems and operators are strictly instructed to
wear protective gear. PO is not purchased directly as a monomer; therefore, consumer exposure is
expected to be negligible. [13]
Health Hazard Information
Acute Effects:
Strong exposure of humans and animals to propylene oxide has caused eye irritation and
respiratory irritation. As a respiratory irritation, cough, dyspnea (shortness of breath), and
pulmonary edema may cause exposure to odors and possibly cause pneumonia. Skin contact, even
with mixed solutions, causes skin irritation and necrosis. Propylene oxide is a stress factor for the
CNS. Excessive exposure to high concentration may cause headaches, motor weakness,
dysfunction, ataxia, and coma in people. Studies involving strong exposure to rats, mice, pigs, and
rabbits have shown propylene oxide to be highly toxic from inhalation, high toxic toxins from the
skin, and moderate to high toxicity from exposure. [14], [15], [16]
Chronic Effects (Noncancer):
The health effects of chronic exposure to propylene oxide in humans have not been documented.
Significant weight loss, increased mortality, and increased incidence of inflammatory lesions in
the nasal cavity, trachea, and lungs have been observed in rats exposed to propylene oxide by
inhalation. Exposure to chronic inhalation of propylene oxide may cause some neuropathological
changes in mice and monkeys [15]
Reproductive/Developmental Effects:
No information is available on the reproductive or developmental effects of propylene oxide in humans.

Studies in mice and rabbits exposed to propylene oxide by inhalation before and during pregnancy
concluded that propylene oxide was harmful to the developing fetus but did not cause birth defects. In
mice, a certain degree of fetotoxicity was observed in all open groups (including a significant decrease
in the number of corpora lutea, tumors, and live infants) and minor bone deformities in others; there
was no maternal death. Increased resorption in waste is seen in rabbits [15]
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Mitigation Measures for Health
The preventive measures used are as follows: [17]

 All staff in plant construction, processing, management and delivery of PO must be
properly trained to be able to deal with most situations.
 When taking a PO sample, use closed sampling systems to prevent air ingress, pollution
and ultimately reduce staff exposure. To prevent over-pressure of the PO, sample
containers should be kept below 32 ℃ below the PO boiling point.
Mitigation measures during transport
 When transporting PO, any equipment involved should be kept under inert nitrogen / PO
vapor pressure and all connectors should be tightly closed to prevent air ingress. [18]
Air Pollution
Propylene oxide is introduced into the atmosphere through evaporation and emissions from
production facilities, and during handling, storage and transportation. Once released into the
atmosphere, PO mixes with hydroxyl radicals producing form anhydride, formaldehyde, acetyl
formyl oxide, and methyl glyoxal which is eventually reduced to carbon dioxide and water.
Mitigation of Air pollution
 The installation of an appropriate ventilation system and fans will be ensured to reduce the
chances of exposure to the environment; this will also reduce the severity of health effects
 It has been found that plants can filter certain pollutants by absorption, growth and
metabolism. Thus, plants serve as an important source of air pollution. In addition, urban
vegetation can help reduce the effect of urban heat
 Pollution control measures should be used regularly [18]
Water and Soil Pollution
When PO is released into the water by leakage or by washing of rain, it hydrolyzes immediately
with acid- or base-catalysis to form propylene glycol, due to the high solubility of PO in water.
The hydrolysis reaction has a half-life of 11 to 22 days which means that PO does not persist in
aquatic environments considering its ability to decompose rapidly. Also, propylene glycol has a
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short shelf life of 1 to 5 days in water as it is easily digested by bacteria once released from the
environment.
Studies have shown that PO is not expected to be advertised on the ground or in the ground as it
has a half-life of 182 days and 365 days, respectively. [19]
Mitigation of Soil and Water Pollution
Potential pollution of soil and groundwater due to spillage or PO leakage can be reduced by:
 Reduce the number of valves, flanges, and couplings in pipes.
 Installing curbs designed to slide away from potential spills to the sump of the collection
 Creating immovable content areas and over-measuring volume to handle the worst PO
emissions.
 Pour residue with water to the sump for further treatment and disposal while the vapor must
be cleaned of nitrogen. Treatment options include biological treatment to minimize spillage
and burn of contaminated soil and liquid PO. However, these treatments should be
consulted with local authorities and comply with environmental regulations.
Mitigation of Spill, Leakage and Fire
 An inspection and maintenance system should be set up for essential equipment such as
tanks, gas test kits, pumps, safety assists, etc. This will increase the duration of the goods
while reducing the risk of spills, leaks, and fires. [18]
References
[1] G. Towler and R. Sinnott, Chemical engineering design: principles, practice and
economics of plant and process design. Butterworth-Heinemann, 2021.
[2] G. Stephanopoulos, Chemical process control. Prentice hall Englewood Cliffs, NJ, 1984.
[3] P. S. Buckley, W. L. Luyben, and J. P. Shunta, Design of distillation column control
systems. Elsevier, 1985.
[5] C. A. Ericson, Hazard analysis techniques for system safety. John Wiley & Sons, 2015.
119 | P a g e
[6] S. Chandrasekaran, Health, safety, and environmental management in offshore and

petroleum engineering. John Wiley & Sons, 2016.
[7] M. E. C. Max Finlayson, Kenneth Irvine, Robert J. McInnes, Beth A. Middleton, Anne A.
van Dam, Nick C. Davidson, The Wetland Book :Structure and Function, Management and
Methods. Springer, 2016.
[8] J. Glasson, R. Therivel, and A. Chadwick, Introduction To Environmental Impact
Assessment. Taylor & Francis, 2005.
[9] Dr. Abdul Majeed and Anwar Kamal: GWADAR: Integrated Development Vision.
Government of Balochistan and IUCN Pakistan, 2007.
[10] highspeedtraining.co.uk/hub/pollution-from-construction/. High Speed Training UK.
[11] aquabarrier.com/blog/information/decrease-environmental-impact-construction/. Aqua
Barrier
[12] E. Peris, "Environmental noise in Europe: 2020," Eur. Environ. Agency, vol. 1, p. 104,
2020.
[13] E. C. Center, Methyloxirane (Propylene Oxide). . Ispra: Special Publication, 2002.
[14] U. D. o. Health and H. Services, "Hazardous substances data bank (HSDB, online
database)," National Toxicology Information Program, National Library of Medicine,
Bethesda, MD, 1993.
[15] U.S. Environmental Protection Agency. Integrated Risk Information System (IRIS) on
Propylene Oxide. National Center for Environmental Assessment, Office of Research and
Development, Washington, DC, 1999.
[16] E. P. s. G.D. Clayton and F.E. Clayton, Industrial Hygiene and Toxicology. , 3rd ed. John
Wiley & Sons, New York. , 1981.
[17] DOW, Propylene Oxide, Storage and Handling Guidelines. . DOW Chemical Company.,
2007.
[18] J. Chen, "Direct Propene Epoxidation over Gold–Titania Catalysts: Kinetics and
Mechanism," 2013.
[19] A. Datta, Process engineering and design using visual basic. CRC press, 2007.
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CHAPTER 6: ECONOMICS OF PLANT
6.1. Introduction
Before beginning process development, at various stages of its development, and before attempting
process and plant design, process engineers must perform an economic evaluation. The evaluation
determines whether they should embark on the project, abandon it, continue it (but with further
research), or transition it to a pilot phase. If they decide to continue developing the process, the
economic evaluation will identify those parts of the process that require further study. Winter [1]
stated that the economic evaluation of a project is a continuous procedure. As the process engineer
gathers new information, he can make a more accurate evaluation followed by a review of the
project to determine if it should continue. [2]
Even if there is insufficient technical information to fully design the facility, we must perform an
economic evaluation to determine whether it is economically and financially feasible. A project is
economically feasible when it is more profitable than other competing projects, and financially
feasible when management can obtain the capital to implement it. Although calculations may show
that a given project could be extremely profitable, the capital requirements may strain the financial
capabilities of the organization. In this case, the project may be abandoned if no partners are found
to share the risk. The economic evaluation of the process takes place in several steps [1]. These
are:
1. Preparation of process flowchart
2. Calculation of mass and energy flows
3. Sizing of main devices
4. Capital cost estimate
5. Estimation of production costs
6. Product sales price forecast
7. Estimated return on investment
The Engineer’s Role in Profit Creation
 They create opportunity for new sales by developing new or improved products. In
addition, they develop the processes that produce these products. [3]
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 They create an opportunity to reduce costs by developing processes that reduce costs.
 They design and build or modify plants or processes that:
1. Produce new or improved products
2. Increase production capacity, which will allow for increased sales
3. Reduce expenses
Capital Requirements
Capital investment in the manufacturing industry is required for brand new plants, for
modifications to existing plants, and even for minor changes to maintain the plant during its
operational life. Investments in new projects can represent huge sums. Plant modifications or
rebuilds are often necessary to accommodate changes in technology, raw material or product
quality specifications, reduce operating costs, meet changing safety and environmental legislation,
and increase production capacity. Renovation projects typically involve spending in the tens of
millions of dollars. The investment required just to maintain the existing plant is slightly smaller,
but still represents an ongoing commitment. [4]
Capital requirements for process plants can be classified under the following categories:
 Land, where the investment is potentially recoverable at the end of the project life, though
expenditure may be incurred in site remediation.
 Fixed capital investment into plant and buildings, which generally has negligible recovery
value (relative to initial investment) at the end of the project life.
 Start-up capital, which is spent during plant commissioning and is nonrecoverable.
 Working capital, which represents investment into stocks of feedstocks and products
essential for plant operability and extended credit to customers, all of which is essentially
recoverable at the end of the project life.
Cost Escalation
All cost estimation methods use historical data and are themselves forecasts of future costs. Prices
of construction materials and labor costs are subject to inflation. Some method must be used to
update old cost data for use in design phase estimation and to forecast future plant construction
costs. The method typically used to update historical cost data uses published cost indices. These
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relate current costs to past costs and are based on data on labor, material and energy costs published
in government statistical reviews. [5]
𝐶𝑜𝑠𝑡 𝐼𝑛𝑑𝑒𝑥 𝑖𝑛 𝑦𝑒𝑎𝑟 𝐴
𝐶𝑜𝑠𝑡 𝑖𝑛 𝑦𝑒𝑎𝑟 𝐴 = 𝐶𝑜𝑠𝑡 𝑖𝑛 𝑦𝑒𝑎𝑟 𝐵 ×
𝐶𝑜𝑠𝑡 𝑖𝑛𝑑𝑒𝑥 𝑖𝑛 𝑦𝑒𝑎𝑟 𝐵
To obtain the best estimate, each job should be broken down into its components and separate
indexes should be used for labor and materials. It is often more convenient to use composite
indexes published for different industries in trade journals. These are weighted average indexes
combining various cost components in ratios considered typical for a particular industry.
Cash Flow
Cash flow is the lifeblood of any commercial organization. Cash flows in a manufacturing
company can be compared to material flows in a manufacturing plant. [6]
Inputs are money needed to pay for research and development; design and construction of
facilities; and plant operation. Outputs are goods for sale; and cash proceeds are recycled into the
organization from the profits earned. "Net cash flow" at any given time is the difference between
income and expenses.
Rate of Return (ROR)
The rate of return (ROR), which is the ratio of annual profit to investment, is a simple index of the
performance of the money invested. Although a simple concept in principle, the calculation of
ROR is complicated by the fact that the annual profit (net cash flow) will not be constant over the
life of the project. The simplest method is to base the ROR on the average income over the life of
the project and the original investment. [6]
Pay-Back Time
The payback period is the time required after the start of the project to pay back the initial
investment from income. Payback period is a useful criterion for judging projects that have a short
life or when capital is only available for a short time. It is often used to assess small improvement
projects on operational equipment. Typically, such projects are expected to have a payback period
of 2 to 5 years. The payback period as a criterion of investment performance inherently does not
consider the performance of the project after the payback period. [6]
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Turnover Ratio
A rapid evaluation method suitable for order of magnitude estimates is known as the turnover ratio
method. The turnover ratio is defined as the ratio of gross annual sales to fixed-capital investment.
𝐺𝑟𝑜𝑠𝑠 𝑎𝑛𝑛𝑢𝑎𝑙 𝑠𝑎𝑙𝑒
𝑇𝑢𝑟𝑛𝑜𝑣𝑒𝑟 𝑟𝑎𝑡𝑖𝑜 =
𝑓𝑖𝑥𝑒𝑑 𝑐𝑎𝑝𝑖𝑡𝑎𝑙 𝑖𝑛𝑣𝑒𝑠𝑡𝑚𝑒𝑛𝑡
where the product of the annual production rate and the average selling price of the commodities
is the gross annual sales figure. The reciprocal of the turnover ratio is sometimes called the capital
ratio or the investment ratio. Turnover ratios of up to 4 are obtained for some business
establishments while some are as low as 0.2. For the chemical industry, as a very rough rule of
thumb, the ratio can be approximated as 0.5. [7]
Manufacturing Costs
All expenses directly connected with the manufacturing operation or the physical equipment of a
process plant itself are included in the manufacturing costs. [7]
These expenses, as considered here, are divided into three classifications:
1. Variable production costs
2. Fixed charges
3. Plant overhead costs
6.2. Estimating Purchased Equipment Costs
The factorial method of cost estimation is based on purchased equipment costs and therefore
requires good estimates for equipment costs. Costs of single pieces of equipment are also often
needed for minor revamp and de-bottlenecking projects. The best source of purchased equipment
costs is recent data on actual prices paid for similar equipment. Engineers working for Engineering,
Procurement, and Construction (EPC) companies (often referred to as contractors) have access to
large amounts of high-quality data, as these companies carry out many projects globally every
year. Engineers working in operating companies may have access to data from recent projects, but
unless they work for a large company that carries out many capital projects, they are unlikely to
be able to develop and maintain current cost correlations for more than a few basic equipment
types. Most large companies recognize the difficulty of making reliable cost estimates and employ
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a few experienced cost engineering specialists who collect data and work closely with the EPC
companies on project budgets. Actual prices paid for equipment and bulk items may differ
substantially from catalog or list prices, depending on the purchasing power of the contractor or
client and the urgency of the project. Discounts and surcharges are highly confidential business
information and will be closely guarded even within EPC companies. [8]
Cost Estimation of Reactor
 Costs for tubular flow reactors with internal tubes can often be estimated by considering
the reactor unit as equivalent to a heat exchanger. [7]
 Area required for heat transfer in reactor = 287.35 m 2 = 3092.93 ft2
 From figure [9] Price of Reactor = $50,000.00
 Module factor = 1
 Fixed tube sheet factor = 1.79
 Material factor = 3.4765
 Pressure factor = 1
 Cost = $311,155.39
 Cost Index in 1987 = 320 [9]
 Cost Index in 2022 = 806.9 [10]
 After Extrapolation Cost index in 2025 = 869
 Expected Cost of Reactor in 2025 = $844,981.36
Cost Estimation of Distillation Column
Cost of Shell
 C = a + bS [8]
 where C = equipment cost, S = Shell mass (kg), a = −10000, b = 600, n = 0.6
 Shell mass = πD L t ρ [8]
 D = Diameter of Column = 1.66 m
 L = Length of Column = 22.198 m
 t = thickness = 0.02 m
 ρ = Density of material 8000 kg/m3 [8]
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 Shell mass = 18512.78 kg

 So, Cost of Column = $208,089.22
Cost of Trays
 C = a + bS [8]
 where C = equipment cost, S = diameter = 1.66m , a = 100, b = 120, n = 2 [8]
 Cost of 1 tray = $430.67
 Cost of 72 trays = $31,008.38
Cost of Whole Distillation Column
 Cost = $239,097.60
 Cost Index in 2006 = 478.6
 Cost Index in 2022 = 806.9 [10]
 Expected Cost in 2025 = $434,132.50
Cost Estimation of Stripper
 The cost of stripper can be estimated is the same manner as for the distillation column
because the stripper of this plant is tray type.
 So, the cost of stripper is taken same as for distillation column with 10% margin.
Cost Estimation of Flash Column
 C = a + bS [8]
 where C = equipment cost, S = Shell mass (kg), a = −15000, b = 560, n = 0.6
 Shell mass = πD L t ρ [8]
 D = Diameter of Column = 0.6 m
 L = Length of Column = 5.7 m
 t = thickness = 0.02 m
 ρ = Density of material 8000 kg/m3
 Shell mass = 1718.208 kg
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 So, Cost of Column = $33,891.51

 Cost Index in 2006 = 478.6 [8]
 Cost Index in 2022 = 806.9 [10]
 Expected Cost in 2025 = $61,537.24
Cost Estimation of Heat Exchanger

 C = a + bS [8]
 where C = equipment cost, S = Area = 5.6 m , a = 500, b = 1100, n = 1 [8]
 So, Cost = $6,660.00
 Cost Index in 2006 = 478.6 [8]
 Cost Index in 2022 = 806.9 [10]
 Expected Cost in 2025 = $12,092.65
Cost Estimation of Pump
 C = a + bS
 where C = equipment cost, S = flowrate = 3.88 L/s, a = 3300, b = 48, n = 1.2 [8]
 So, Cost = $3,544.25
 Cost Index in 2006 = 478.6 [8]
 Cost Index in 2022 = 806.9 [10]
 Expected Cost in 2025 =$6,435.34
Cost Estimation of Mixer
 C = a + bS [8]
 where C = equipment cost, S = flowrate = 8.75 L/s, a = 780, b = 62, n = 0.8 [8]
 So, Cost = $1,131.56
 Cost Index in 2006 = 478.6 [8]
 Cost Index in 2022 = 806.9 [10]
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 Expected Cost in 2025 = $2,054.59
Total Equipment Cost
Dollar rate in mid of 2019 = 158 Rs.

Current rate of dollar = 230 Rs.
After extrapolation expected dollar rate for 2025 = 302 Rs.
Table 6-1 All Equipment Capital Cost
Name of Number of Cost of one Total cost ($) Total Cost

equipment equipment equipment ($) (MRs.)
Pump 6 $6,435.34 $38,612.06 11.66
Heat Exchanger 3 $12,092.65 $36,277.94 10.96
Mixer 1 $2,054.59 $2,054.59 0.62
Reactor 1 $844,981.36 $844,981.36 255.18
Flash Column 1 $61,537.24 $61,537.24 18.58
Stripper 1 $477,545.75 $477,545.75 144.22
Distillation 2 $434,132.50 $868,265.00 262.22
Column
Total $2,329,273.93 703.44
equipment cost
6.3. Fixed Capital Investment
As the equipment cost is 22% of Fixed Capital Investment [7]

So, Fixed Capital Investment (FCI) = $10,587,608.79 = 3197.46 million Rs.
6.4. Direct Cost

Table 6-2 Direct Cost
Components Estimated Cost ($) Estimated Cost (MRs.)

Purchased Equipment 22% of FCI $2,329,273.93 703.44
Installation 8% of FCI $847,008.70 255.80
Instrumentation cost 9% of FCI $952,884.79 287.77
Piping 7% of FCI $741,132.62 223.82
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Electrical system 4.6 % of FCI $487,030.00 147.08

Buildings 4.6% of FCI $487,030.00 147.08
Yard improvement 1.8% of FCI $190,576.96 57.55
Service facilities 13.8 % FCI $1,461,090.01 441.25
Land 2% of FCI $211,752.18 63.95
Total $7,707,779.20 2327.75
6.5. Indirect Cost
Table 6-3 Indirect Cost
Components Estimated Cost ($) Estimated Cost (MRs.)

Engineering and Supervision 7.3% of FCI $772,895.44 233.41
Construction Expense 9% of FCI $952,884.79 287.77
Legal Expense 1.8% of FCI $190,576.96 57.55
Contractors Fee 1.8% of FCI $190,576.96 57.55
Contingency 7.3% of FCI $772,895.44 233.41
Total $2,879,829.59 869.71
6.6. Working Capital Investment
WCI = 15% of TCI [7]

TCI = FCI/0.85
WCI = $1,868,401.55 = 564.26 million Rs.
6.7. Total Capital Investment
Total Capital Investment = WCI + FCI [7]

Total Capital Investment = $12,456,010.34 = 3761.72 million Rs.
6.8. Total Product Cost
Assume that FCI depreciate by straight line method for 15 years assuming 5% of salvage
value at the end of plant life
Depreciation = D = (v-vs)/N [7]
V = FCI = $10,587,608.79 = 3197.46 million Rs.
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Vs = 0.05 *$10,587,608.79 =$529,380.44 = 159.87 million Rs.

N = No. of years = 15
D = $670,548.56 = 202.51 million Rs.
Product cost = TCI – D = $11,785,461.79 = 3559.21 million Rs.
Fixed charges =12% of PC= $1,414,255.41 = 427.11 million Rs.
Direction production cost = 55% of PC= $6,482,003.98 = 1957.57 million Rs.
Plant overhead =10% of PC= $1,178,546.18 = 355.92 million Rs.
Total manufacturing cost = Fixed charges + direct production cost + plant overhead [7]
Total manufacturing cost = $9,074,805.57 = 2740.59 million Rs.
6.9. Raw Material Cost
Expected Cost of Propylene = 0.8 $/kg

Total kg required for 1 year (300 days) = 47874881.63
Total cost of propylene for 1 year = $38,299,905.30 = 11,566.57 million Rs.
Expected cost of Hydrogen Peroxide = 0.62 $/kg
Total kg required for 1 year (300 days) = 38504661.26
Total cost of propylene for 1 year = $23,872,889.98 = 7,209.61 million Rs.
Total Raw material cost/Year = $62,172,795.28 = 18,776.18 million Rs.
Admin cost = 5% of PC = $589,273.09 = 177.96 million Rs.
Distribution and selling cost = 18% of PC = $2,121,383.12 = 640.66 million Rs.
Research and development cost=5% of PC = $589,273.09 = 177.96 million Rs.
Financing =6% of PC = $707,127.71 = 213.55 million Rs.
6.10. General Expenses
Total product cost = M.C. + G.E [7]

General Expense = $4,007,057.01 = 1,210.13 million Rs.
6.11. Gross Earning/Income

Sale of Propylene oxide = 2.5 $/kg
Total income of per year = $75,000,000.00 = 22,650.00 million Rs.
130 | P a g e
Gross income = $61,918,137.42 = 18,699.28 million Rs.

Tax rate 30% = $18,575,441.23 = 5,609.78 million Rs.
6.12. Net Profit

Net Profit = Gross Income – Taxes [7]
Net Profit = $43,342,696.19 = 13,089.49 million Rs.
6.13. Rate of Return

Rate of Return = (Net Profit/Total Investment) = 34.79 %
6.14. Payback Period

Payback period = 1/ ROR [7]
Payback Period = 2.87 years
References
[1] O. Winter, "Preliminary economic evaluation of chemical processes at the research level,"
Industrial & Engineering Chemistry, vol. 61, no. 4, pp. 45-52, 1969.
[2] H. Silla, Chemical process engineering: design and economics. CRC Press, 2003.
[3] T. Brown, Engineering economics and economic design for process engineers. CRC Press,
2016.
[4] D. J. Brennan, Process industry economics: an international perspective. IChemE, 1998.
[5] G. Towler and R. Sinnott, Chemical engineering design: principles, practice and economics
of plant and process design. Butterworth-Heinemann, 2021.
[6] R. K. Sinnott, J. M. Coulson, and J. F. Richardson, Chemical engineering design (no. 4).
Elsevier Butterworth-Heinemann Oxford, 2005.
[8] G. TOWLER and R. SINNOTT, "CHEMICAL ENGINEERING DESIGN Principles, Practice
and Economics of Plant and Process Design," 2008.
[9] D. E. Garrett, Chemical engineering economics. Springer Science & Business Media, 2012.
[10] toweringskills.com/financial-analysis/cost-indices/ CEPI. ToweringSkills, 2022.
131 | P a g e

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Production Of 100 MTPD Of Epoxy Propane

Using Propene and Oxygenated Water by

Muhammad Hafeez Rasheed 2018-CH-01

Department of Chemical Engineering & Technology

Production Of 100 MTPD Of Epoxy Propane

Muhammad Hafeez Rasheed 2018-CH-01

Department of Chemical Engineering & Technology

GracIous, the most mercIfuL

Propylene oxide is frequently employed as a chemical intermediary in the synthesis of

CHAPTER 1: INTRODUCTION .....................................................................................1

1.1. Introduction ............................................................................................................. 1

1.2. Propylene Oxide ...................................................................................................... 1

1.3. Uses of Propylene Oxide ......................................................................................... 2

1.4. Chemical Properties ................................................................................................ 2

1.5. Physical Properties .................................................................................................. 4

1.6. Thermodynamic Properties ..................................................................................... 4

1.7. Propylene (Reactant) ............................................................................................... 4

1.8. Availability of Propylene ........................................................................................ 5

1.9. Hydrogen Peroxide (Oxidizing Reactant) ............................................................... 5

1.10. Properties of Hydrogen Peroxide .......................................................................... 6

1.11. Availability of Hydrogen Peroxide ....................................................................... 6

1.12. Methanol (Solvent) ................................................................................................ 7

1.13. Propylene Glycol (Side Product) ........................................................................... 7

1.14. Titanium-Silicalite TS-1 (Catalyst) ....................................................................... 7

Application (Catalyst) .................................................................................... 8

1.15. Market Analysis .................................................................................................... 8

Top Exporters of Methyloxirane (Propylene Oxide) in 2020 ........................ 9

Worldwide Major Propylene Oxide Production Companies ....................... 10

1.16. Market of Propylene Oxide in China .................................................................. 11

China Imports of Propylene Oxide .............................................................. 11

China Import of Propylene Oxide in USD/Year .......................................... 11

China Import of Propylene Oxide in Tons/Year .......................................... 12

1.17. Capacity Selection ............................................................................................... 12

CHAPTER 2: LITERATURE REVIEW ......................................................................14

2.1. Chlorohydrin Process ............................................................................................ 14

2.2. The Indirect Oxidation Processes .......................................................................... 15

Oxidation of Isobutane to T-butyl Hydroperoxide and T-butyl Alcohol ...... 15

Ethylbenzene Hydroperoxide Process ........................................................... 17

Other Indirect Oxidation Processes ............................................................... 18

2.3. Direct Oxidation Processes ................................................................................... 18

2.4. Hydrogen Peroxide Process (HPPO) ..................................................................... 19

2.5. Patented Silver-Based Catalyst Process ................................................................ 20

2.6. Process Selection ................................................................................................... 22

2.7. Rate Laws .............................................................................................................. 22

Effect of Methanol (Solvent) ......................................................................... 22

Effect of Pressure ........................................................................................... 23

Effect of Temperature .................................................................................... 23

Process Flow Diagram ................................................................................... 24

2.9. Process Description ............................................................................................... 25

Process Overview .......................................................................................... 25

2.10. Detailed Process Description............................................................................... 26

Feed Preparation .......................................................................................... 26

Pre-Separation Section ................................................................................. 27

Propylene Oxide Distillation Column.......................................................... 28

Methanol-Water Distillation Column .......................................................... 28

CHAPTER 3: LAW OF CONSERVATIONS...............................................................30

3.1. Conservation of Mass ............................................................................................ 30

Basis for Calculations .................................................................................... 30