PROJECT Acrylic Acid

King Saud University
College of Engineering
Chemical Engineering Department
Graduation Project 1435-1436
ChE 422 Selected Topics in Chemical Engineering
Production of Acrylic Acid from Propylene
Prepared By
Nasser Mansour Alsubaie (431101932) Husam Fahad Alkhodairi (431101335)
Saud Abdullah Alhagbani (431104454) Abdullah Saleh Altorbaq (431102801)
2nd Semester
1435-1436 (2014-2015)
Project Statement
ChE 422 Selected Topics in Chemical Engineering (2014 2015)
Project Title
Introduction
Acrylic acid is an organic compound with the formula CH2CHCO2H. It is the simplest
unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid
terminus. This colorless liquid has a characteristic acrid or tart smell. It is miscible with water,
alcohols, ethers, and chloroform. More than one billion kilograms are produced annually. It is
polymerized to form polyacrylic acid.
Objectives
In this project, a group of four students work together to design a plant for the production of
acrylic acid. All process units within the plant must be designed such that the final proposed
process can be adopted by external investors. Profitability analysis must be carried out in a
sense of obtaining the most suitable selling price.
General Tasks and Requirements
The authors of this project report are asked to do the following:
Perform extensive literature survey regarding the uses and applications of acrylic acid
Perform extensive literature survey regarding the already-existing processes
Carry out multiple-criteria decision analysis to determine the best production process
Make modifications to the selected production process (if necessary)
Perform a HAZOP study
Carry out complete design calculations of major process equipment
Perform control loops on equipment units
Estimate capital investment and manufacturing costs and carry out profitability analysis
Carry out plant location study
Carry out plant layout study
Executive Summary
This project is concerned with the design of an acrylic acid plant with a production capacity of
100,000 tons per year. Chapter one gives the reader an insight to the importance of acrylic acid
in todays global market by highlighting its role in the production of other chemicals. Chapter
two is devoted to discussing the various production processes of acrylic acid and selecting the
best process based on multiple-criteria decision analysis. The results of the analysis indicate
that production from propylene is the best production process gaining a total of 730 points out
of 750. Chapter three discusses the environmental worries associated with running an acrylic
acid plant, as well as providing two different cases of previous acrylic acid plant accidents. In
addition, chapter three compares the plants emission levels against the limits set by the Royal
Commission for Jubail and Yanbu (RCJY). Chapter four carries out HAZOP analysis for the
process for a selected number of equipment. Chapter five presents complete design calculations
for the major equipment involved in the process. These include, but are not limited to,
distillation columns, heat exchangers, reactors, absorbers, etc. Chapter six discusses the control
systems used in the acrylic acid process. Chapter seven estimates the fixed capital cost as well
as the manufacturing costs associated with running the plant. The fixed capital cost amounted
to $6,880,191.59 (25,800,718.46 SR) and the manufacturing costs amounted to
$91,001,702.55/year (341,256,384.56 SR/year). Chapter seven also carries out profitability
analysis for determining the optimum selling price based on a rational payback period and an
attractive net present value. Three prices have been investigated, 2.20% greater than the
manufacturing costs, 2.75% greater than the manufacturing costs, and 1.60% greater than the
manufacturing costs. The results of the analysis concluded that the first case (i.e. 2.20% greater
than the manufacturing costs) would be the best economical option and therefore was selected.
The corresponding selling price would be $930/ton (3,487.5 SR/ton) for a discounted interest
rate of 12%. Chapter eight is devoted to finding the best site location as well as providing the
plant layout. Two competing locations for the plant site were investigated: Jubail Industrial
City and Yanbu Industrial City. The decision of selecting the best option was again based on
the multiple-criteria decision analysis method. The results of the analysis concluded that Jubail
Industrial City would be the best option, scoring a total of 149/180 compared to Yanbus
140/180.
Keywords: Acrylic Acid, Acetic Acid, Propylene
ii
Commented [HA1]:
Acknowledgments
The students working on this project spent huge amounts of time and commitment to produce
this writing in its final form. Still, this would not have been possible without the help and
guidance of our teachers, Dr. Mourad Boumaza, Dr. Mohanad Elharbawi, Dr. Mohammad Asif,
Dr. Mohammad El-Bashir, and Dr. Saleh Al-Arni.
Thanks are extended to Eng. Yousef Ashraf as well for his valuable remarks, tutorials, and for
providing us with useful resources. The authors would like to extend their gratitude to all the
instructors and engineers within the department who have helped us during the early stages of
the project.
We would like to thank our colleagues from SABICs Plastics Applications Development
Center, especially Eng. Mansour Al-Qoblan, who provided us with the insight and know-how
that significantly helped in finalizing this project.
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Table of Contents
PROJECT STATEMENT ................................................................................................................................. I
EXECUTIVE SUMMARY ............................................................................................................................... II
ACKNOWLEDGMENTS .............................................................................................................................. III
LIST OF FIGURES ..................................................................................................................................... XIV
LIST OF TABLES ........................................................................................................................................ XV
NOMENCLATURE .................................................................................................................................... XVI
1.1
OVERVIEW ....................................................................................................................................... 1
1.2
BRIEF HISTORY ................................................................................................................................. 2
1.3
USES AND APPLICATIONS .................................................................................................................. 3
1.4
PHYSICAL AND CHEMICAL PROPERTIES OF ACRYLIC ACID ................................................................... 4
1.4.1
PHYSICAL PROPERTIES ............................................................................................................................... 4
1.4.2
CHEMICAL AND THERMODYNAMIC PROPERTIES .............................................................................................. 5
1.4.3
SAFETY AND TOXICOLOGICAL PROPERTIES ...................................................................................................... 6
1.5
MARKET ANALYSIS ........................................................................................................................... 7
1.5.1
OVERVIEW .............................................................................................................................................. 7
1.5.2
WORLDWIDE PRODUCTION OF ACRYLIC ACID ................................................................................................. 8
1.5.3
WORLDWIDE CONSUMPTION OF ACRYLIC ACID .............................................................................................. 9
1.5.4
PRICES OF ACRYLIC ACID AND ITS RAW MATERIALS ....................................................................................... 10
2.1
PRODUCTION OF ACRYLIC ACID FROM PROPYLENE .......................................................................... 11
2.1.1
BACKGROUND ........................................................................................................................................ 11
2.1.2
REACTOR .............................................................................................................................................. 12
2.1.3
CATALYST .............................................................................................................................................. 12
2.2
PRODUCTION OF ACRYLIC ACID FROM PROPANE ............................................................................. 12
2.2.1
BACKGROUND ........................................................................................................................................ 12
2.2.2
REACTOR .............................................................................................................................................. 13
2.2.3
CATALYST .............................................................................................................................................. 13
2.3
PRODUCTION OF ACRYLIC ACID FROM ACETYLENE ........................................................................... 13
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2.3.1
BACKGROUND ........................................................................................................................................ 13
2.3.2
REACTOR .............................................................................................................................................. 14
2.3.3
CATALYST .............................................................................................................................................. 14
2.4
PROCESS SELECTION ....................................................................................................................... 14
3.1
INTRODUCTION .............................................................................................................................. 19
3.2
INSTABILITY OF ACRYLIC ACID ......................................................................................................... 19
3.3
HEALTH AND SAFETY FACTORS ........................................................................................................ 20
3.3.1
TOXICITY ............................................................................................................................................... 20
3.3.2
INDUSTRIAL HYGIENE .............................................................................................................................. 20
3.3.3
MEDICAL MANAGEMENT ......................................................................................................................... 20
3.3.4
FIRST AID .............................................................................................................................................. 20
3.4
PERSONAL PROTECTIVE EQUIPMENT ............................................................................................... 21
3.5
STORAGE OF ACRYLIC ACID ............................................................................................................. 22
3.6
TRANSPORT AND LOADING/UPLOADING ......................................................................................... 22
3.7
ENVIRONMENTAL CONSIDERATIONS ............................................................................................... 23
3.7.1
WASTE DISPOSAL ................................................................................................................................... 23
3.7.2
AIR EMISSIONS....................................................................................................................................... 23
3.8
PRODUCTION OF ACRYLIC ACID BY PROPYLENE................................................................................ 24
3.8.1
MAXIMUM ALLOWABLE EXPOSURE LIMITS .................................................................................................. 24
3.8.2
TOXICOLOGY / HEALTH EFFECTS / HANDLING / PERSONAL PROTECTION ............................................................ 25
3.9
PREVIOUS INCIDENTS INVOLVING ACRYLIC ACID PRODUCTION ........................................................ 30
3.9.1
NIPPON SHOKUBAI HIMEJI PLANT INCIDENT ................................................................................................ 30
3.9.2
YOKOHAMA CHEMICAL FACTORY ............................................................................................................... 32
4.1
INTRODUCTION .............................................................................................................................. 33
4.2
GUIDE WORDS AND PARAMETERS .................................................................................................. 35
4.3
STUDY NODES ................................................................................................................................ 35
5.1
BACKGROUND OF HEAT EXCHANGERS ............................................................................................. 64
5.1.1
DEFINITION ........................................................................................................................................... 64
5.1.2
FLOW ARRANGEMENT ............................................................................................................................. 64
5.1.3
TYPES OF HEAT EXCHANGERS .................................................................................................................... 64
5.1.3.1
Shell and Tube Heat Exchanger ................................................................................................ 64
5.1.3.2
Plate Heat Exchanger ............................................................................................................... 65
5.1.3.3
Plate and Shell Heat Exchanger ............................................................................................... 65
5.1.3.4
Double Pipe Heat Exchanger .................................................................................................... 66
5.1.3.5
Fluid Heat Exchanger ............................................................................................................... 66
5.1.3.6
Waste Recovery Heat Exchanger ............................................................................................. 66
5.1.4
CLASSIFICATION ACCORDING TO PROCESS FUNCTION..................................................................................... 66
5.1.4.1
Condensers ............................................................................................................................... 66
5.1.4.2
Liquid to Vapor Phase Change Exchangers (Reboilers and Vaporizers) ................................... 68
5.1.5
HEAT EXCHANGER DESIGN EQUATIONS ....................................................................................................... 70
5.1.5.1
Preliminary ............................................................................................................................... 70
5.1.5.2
Tube-Side .................................................................................................................................. 73
5.1.5.3
Shell-Side .................................................................................................................................. 73
5.1.5.4
Overall Coefficient .................................................................................................................... 74
8.4.5.5
Pressure Drop ........................................................................................................................... 74
5.1.6
HORIZONTAL CONDENSER DESIGN EQUATIONS............................................................................................. 76
5.1.6.1
Preliminary ............................................................................................................................... 76
5.1.6.2
Tube-Side .................................................................................................................................. 76
5.1.6.3
Shell-Side .................................................................................................................................. 76
5.1.6.4
Overall Coefficient .................................................................................................................... 77
5.1.6.5
Pressure Drop ........................................................................................................................... 77
5.1.7
THERMOSYPHON REBOILER DESIGN EQUATIONS ........................................................................................... 78
5.1.8
DESIGN ASSUMPTIONS ............................................................................................................................ 79
5.2
SIZING OF COOLER E-302................................................................................................................. 80
5.2.1
PROBLEM STATEMENT ............................................................................................................................. 80
5.2.2
DESIGN CONSIDERATIONS ........................................................................................................................ 80
5.2.3
INLET AND OUTLET STREAMS .................................................................................................................... 81
5.2.4
PHYSICAL PROPERTIES ............................................................................................................................. 82
5.2.5
CALCULATIONS ....................................................................................................................................... 83
5.2.5.1
Preliminary Calculations ........................................................................................................... 83
5.2.5.2 Fluid Allocation and Fouling Factors ............................................................................................... 84
vi
5.2.5.3 Overall Heat Transfer Coefficient Calculations ................................................................................ 84

5.2.6
5.3
SUMMARY............................................................................................................................................. 86
SIZING OF REBOILER E-303 .............................................................................................................. 87
5.3.1
5.3.2
DESIGN CONSIDERATIONS ........................................................................................................................ 87
5.3.3
5.3.4
5.3.5
CALCULATIONS ....................................................................................................................................... 88
5.3.6
SUMMARY............................................................................................................................................. 90
5.4
DESIGN OF CONDENSER E-304 ......................................................................................................... 91
5.4.1
5.4.2
DESIGN CONSIDERATION .......................................................................................................................... 91
5.4.3
5.4.4
5.4.4
CALCULATIONS ....................................................................................................................................... 93
5.4.4.1
Preliminary Calculations (1st Trial) ........................................................................................... 93
5.4.4.2 Tube-Side Calculations (1st Trial) ..................................................................................................... 95

5.4.4.3 Shell-Side Calculations (1st Trial) ..................................................................................................... 95
5.4.4.4 Overall Calculations (1st Trial) ......................................................................................................... 97
5.4.4.5 Preliminary Calculations (2nd Trial) .................................................................................................. 97
5.4.4.6 Tube-Side Calculations (2nd Trial) .................................................................................................... 98
5.4.4.7 Shell-Side Calculations (2nd Trial) ..................................................................................................... 98
5.4.4.8 Overall Calculations (2nd Trial)......................................................................................................... 99
5.4.4.9 Tube-Side Pressure Drop Calculations ........................................................................................... 100
5.4.4.10 Shell-Side Pressure Drop Calculations ......................................................................................... 100
5.4.5
5.5
SUMMARY........................................................................................................................................... 102
DESIGN OF COOLER E-305 ............................................................................................................. 103
5.5.1
PROBLEM STATEMENT ........................................................................................................................... 103
5.5.2
DESIGN CONSIDERATION ........................................................................................................................ 103
5.5.3
INLET AND OUTLET STREAMS .................................................................................................................. 104
5.5.4
PHYSICAL PROPERTIES ........................................................................................................................... 104
vii
5.5.5
CALCULATIONS ..................................................................................................................................... 105
5.5.5.1
Preliminary Calculations (1st Trial) ......................................................................................... 105
5.5.5.2 Tube-Side Calculations (1st Trial) ................................................................................................... 107

5.5.5.3 Shell-Side Calculations (1st Trial) ................................................................................................... 108
5.5.5.4 Overall Calculations (1st Trial) ....................................................................................................... 110
5.5.5.5 Preliminary Calculations (2nd Trial) ................................................................................................ 110
5.5.5.6 Tube-Side Calculations (2nd Trial) .................................................................................................. 111
5.5.5.7 Shell-Side Calculations (2nd Trial) ................................................................................................... 111
5.5.5.8 Overall Calculations (2nd Trial)....................................................................................................... 112
5.5.5.9 Tube-Side Pressure Drop Calculations ........................................................................................... 113
5.5.5.10 Shell-Side Pressure Drop Calculations ......................................................................................... 113
5.5.6
5.6
SUMMARY........................................................................................................................................... 114
BACKGROUND OF DISTILLATION COLUMNS ................................................................................... 116
5.6.1
DEFINITION ......................................................................................................................................... 116
5.6.2
MAIN COMPONENTS OF A DISTILLATION COLUMN ...................................................................................... 116
5.6.3
BASIC OPERATION ................................................................................................................................ 116
5.6.4
REFLUX ............................................................................................................................................... 117
5.6.5
TYPES OF COLUMNS .............................................................................................................................. 118
5.6.5.1
Batch Columns ....................................................................................................................... 118
5.6.5.2
Continuous Columns ............................................................................................................... 119
5.6.6
5.6.6.1
Bubble Cap Trays .................................................................................................................... 119
5.6.6.2
Valve Trays ............................................................................................................................. 120
5.6.6.3
Sieve Trays.............................................................................................................................. 120
5.6.7
5.7
TYPES OF TRAYS ................................................................................................................................... 119
APPLICATIONS OF DISTILLATION............................................................................................................... 120
DESIGN OF DISTILLATION COLUMN T-303 ...................................................................................... 121
5.7.1
5.7.2 COMPOSITION .............................................................................................................................. 121

5.7.3 ASSUMPTIONS ........................................................................................................................................... 122
5.7.4 STAGE EQUILIBRIUM RELATIONS ................................................................................................................... 122
5.7.5 MCCABE-THIELE METHOD .......................................................................................................................... 125
5.7.5.1 Equations for Enriching Section ..................................................................................................... 125
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5.7.5.2
Equations for Stripping Section .............................................................................................. 126
5.7.5.3 Determination of the Minimum Reflux Ratio Rm ........................................................................... 127

5.7.5.4 Determination of Theoretical Number of Trays ............................................................................ 128
5.7.5.5 Determination of the Minimum Number of Trays ......................................................................... 129
5.7.6 CALCULATIONS .......................................................................................................................................... 129
5.7.6.1
Theoretical Number of Stages ................................................................................................ 129
5.7.6.2 Minimum Reflux Ratio Rm............................................................................................................. 130

5.7.6.3 Minimum Number of Stages ......................................................................................................... 131
5.7.6.4 Actual Number of Stages ............................................................................................................... 133
5.7.6.5 Tower Height ................................................................................................................................. 135
5.7.6.6 Tower Diameter............................................................................................................................. 135
5.7.6.7 Tray Selection ................................................................................................................................ 139
5.7.6.8 Tower Material of Construction (MOC) ......................................................................................... 139
5.7.7
5.8
SUMMARY........................................................................................................................................... 140
DESIGN OF ABSORPTION COLUMN T-302 ....................................................................................... 141
5.8.1
5.8.2
FLOWRATE OF INLET AND OUTLET STREAMS .............................................................................................. 141
5.8.3
ASSUMPTIONS ..................................................................................................................................... 142
5.8.4
EQUILIBRIUM LINE ................................................................................................................................ 142
5.8.5
THEORY .............................................................................................................................................. 144
5.8.5.1
Operating Line Derivation ...................................................................................................... 144
5.8.5.2 Graphical Determination of the Theoretical Number of Stages .................................................... 146

5.8.5.3 Analytical Determination of the Theoretical Number of Stages ................................................... 146
5.8.6 CALCULATIONS .......................................................................................................................................... 148
5.8.6.1 Graphical Determination of the Theoretical Number of Stages .................................................... 148
5.8.6.2 Analytical Determination of the Theoretical Number of Stages ................................................... 148
5.8.6.3 Actual Number of Stages ............................................................................................................... 149
5.8.6.4 Minimum Solvent Flow and Maximum Discharge Concentration ................................................. 150
5.8.6.5 Column Height ............................................................................................................................... 151
5.8.6.6 Column Diameter .......................................................................................................................... 151
5.8.6.7 Tray Selection ................................................................................................................................ 155
5.8.6.8 Material of Construction ............................................................................................................... 155
5.8.7
5.9
SUMMARY........................................................................................................................................... 156
BACKGROUND OF REACTORS ........................................................................................................ 158
ix
5.9.1
GENERAL DESCRIPTION .......................................................................................................................... 158
5.9.2
BATCH AND CONTINUOUS FLOW ............................................................................................................. 158
5.9.2.1
Batch Reactors ....................................................................................................................... 158
5.9.2.2
Continuous Reactors .............................................................................................................. 159
5.9.3
TYPES OF CONTINUOUS REACTORS ........................................................................................................... 160
5.9.3.1
Tubular Reactor ...................................................................................................................... 160
5.9.3.2
Fixed Bed Reactor ................................................................................................................... 160
5.9.3.3
Continuous Stirred Tank Reactor (CSTR) ................................................................................ 161
5.10
DESIGN OF REACTOR R-201....................................................................................................... 162
5.10.1
5.10.2
FLOWRATE OF INLET AND OUTLET STREAMS .............................................................................................. 162
5.10.3
ASSUMPTIONS ..................................................................................................................................... 163
5.10.4
THEORY .............................................................................................................................................. 163
5.10.5 REACTION KINETICS .................................................................................................................................. 165

5.10.6
THERMODYNAMIC PROPERTIES ............................................................................................................... 165
5.10.7
DESIGN CALCULATIONS .......................................................................................................................... 167
5.10.7.1 Net Rate Laws ............................................................................................................................. 167

5.10.7.2 Heat of Reactions ........................................................................................................................ 168
5.10.7.3 Energy Balance on Process Stream ............................................................................................. 169
5.10.7.4 Energy Balance on Cooling Medium ............................................................................................ 170
5.10.7.5 Algebraic Equations..................................................................................................................... 170
5.10.7.6 Differential Equations Initial Values ............................................................................................ 171
5.10.7.7 Solving Using Polymaths ODE Solver .......................................................................................... 172
5.10.7.8 Reactor Dimensions ..................................................................................................................... 172
5.10.7.9 Reactor Catalyst .......................................................................................................................... 174
5.10.7.10 Conversion of Propylene ............................................................................................................ 175
5.10.7.11 Yield ........................................................................................................................................... 175
5.10.7.12 Selectivity .................................................................................................................................. 175
5.10.7.13 Space time ................................................................................................................................. 176
5.10.7.14 Material of Construction ........................................................................................................... 176
5.10.8
6.1
SUMMARY........................................................................................................................................... 177
INTRODUCTION ............................................................................................................................ 179
6.1.1
DEFINITION ......................................................................................................................................... 179
6.1.2
CONTROL TERMINOLOGY ....................................................................................................................... 180
6.1.3
PROCESS CONTROL OBJECTIVES ............................................................................................................... 181
6.1.4
TYPES OF CONTROL SYSTEMS .................................................................................................................. 182
6.2
ACRYLIC ACID PLANT CONTROL SYSTEMS ...................................................................................... 183
6.2.1
R-301: REACTOR ................................................................................................................................. 183
6.2.2
T-303: DISTILLATION COLUMN ............................................................................................................... 184
6.2.3
T-302: ABSORBER TOWER ..................................................................................................................... 186
6.2.4
HEAT EXCHANGERS ............................................................................................................................... 187
7.1
INTRODUCTION ............................................................................................................................ 191
7.2
ESTIMATION OF PURCHASED EQUIPMENT COST ............................................................................ 192
7.3
EFFECT OF TIME ON PURCHASED EQUIPMENT COST....................................................................... 193
7.4
BARE MODULE COST OF EQUIPMENT AT BASE CONDITIONS ........................................................... 194
7.5
BARE MODULE COST OF EQUIPMENT AT OPERATING CONDITIONS ................................................. 195
7.6
GRASSROOTS COST....................................................................................................................... 197
7.7
CALCULATIONS ............................................................................................................................. 197
7.7.1
E-302 ................................................................................................................................................ 197
10.7.2
E-303 ................................................................................................................................................ 198
7.7.3
E-304 ................................................................................................................................................ 199
7.7.4
E-305 ................................................................................................................................................ 200
7.7.5
T-302 ................................................................................................................................................ 201
7.7.6
T-303 ................................................................................................................................................ 202
7.7.7 R-301 ..................................................................................................................................................... 203

7.7.8 GRASSROOTS COST .................................................................................................................................... 204
7.8
INTRODUCTION ............................................................................................................................ 207
10.9
OPERATING LABOR COSTS ........................................................................................................ 209
7.10
UTILITY STREAMS COSTS .......................................................................................................... 210
7.11
RAW MATERIALS COSTS ........................................................................................................... 211
7.12
MANUFACTURING COSTS CALCULATIONS ................................................................................. 212
xi
7.12.1 OPERATING LABOR ................................................................................................................................... 212

7.12.2 UTILITY STREAMS ..................................................................................................................................... 212
7.12.3 RAW MATERIALS ..................................................................................................................................... 213
7.12.4 TOTAL MANUFACTURING COSTS ................................................................................................................. 214
7.13
SELLING PRICE .......................................................................................................................... 216
7.14
PROJECT LIFE............................................................................................................................ 216
7.15
CASH FLOW AND INTEREST RATE .............................................................................................. 216
7.16
TAXATION AND DEPRECIATION ................................................................................................. 217
7.17
CASH FLOW DIAGRAM FOR A NEW PROJECT ............................................................................. 218
7.18
PROFITABILITY CRITERIA FOR PROJECT EVALUATION ................................................................. 219
7.18.1 NON-DISCOUNTED PROFITABILITY CRITERIA .................................................................................................. 219

7.18.2 DISCOUNTED PROFITABILITY CRITERIA .......................................................................................................... 220
7.19 ANALYSIS AND CALCULATIONS ....................................................................................................... 220
7.19.1 Case One ........................................................................................................................................ 221
7.19.2 Case Two ........................................................................................................................................ 224
7.19.3 Case Three ...................................................................................................................................... 227
7.19.4 Selling Price Analysis ...................................................................................................................... 229
8.1
SITE LOCATION ............................................................................................................................. 231
8.1.1
INTRODUCTION .................................................................................................................................... 231
8.1.2
OVERVIEW OF POSSIBLE SITES ................................................................................................................. 233
8.1.3
SITE SELECTION .................................................................................................................................... 234
8.2
PLANT LAYOUT ............................................................................................................................. 237
CONCLUSIONS ....................................................................................................................................... 241

RECOMMENDATIONS ............................................................................................................................ 242
REFERENCES .......................................................................................................................................... 243
APPENDIX 1 .......................................................................................................................................... 248
APPENDIX 2 .......................................................................................................................................... 255
APPENDIX 3 .......................................................................................................................................... 257
ATTACHMENTS ..................................................................................................................................... 263
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xiii
Commented [HA2]:
List of Figures
xiv
Commented [HA3]:
List of Tables
xv
Commented [HA4]:
Nomenclature
xvi
Chap te r One : In trod uc tion
CHAPTER ONE
Introduction
1.1
Overview
Acrylic acid is an organic compound with the formula CH2CHCO2H. It is the simplest
unsaturated carboxylic acid, consisting of a vinyl group connected directly to a carboxylic acid
terminus. This colorless liquid has a characteristic acrid or tart smell. It is miscible with water,
alcohols, ethers, and chloroform. More than one billion kilograms are produced annually. It is
polymerized to form polyacrylic acid [1].
At room temperature, acrylic acid is a corrosive, colorless liquid with a pungent odor. It has a
boiling point of 141 C and a freezing point of 13 C at normal pressure. It mixes readily with
water, alcohols and common organic solvents. Glacial acrylic acid is typically min. 99.5% pure
with water content less than 0.3% and acrylic acid dimer less than 0.1% [1]. Because of its
reactive polymerization potential, acrylic acid is normally shipped with a polymerization
inhibitor such as monomethyl ether of hydroquinone or phenothiazine.
Acrylic acid is an essential polymer raw material for many industrial and consumer products.
Currently, acrylic acid is manufactured from propylene, which is created as a byproduct from
fossil fuels manufacture and industrial cracking of heavy hydrocarbons. However, the
discovery of new natural gas reserves presents new opportunities for the production of acrylic
acid.
Acrylic acid has been in production for nearly 30 years [2]. Demand for acrylic acid is
increasing year on year due to its various end users in superabsorbent, adhesive, surface
coating, etc. Acrylic acid market has huge potential in the future, as it would create a range of
applications, namely in industries such as surfactants industry, surface coatings industry,
adhesives and sealants industry, plastic additives and co-monomers, etc.
Table 1.1 Formula and structure of acrylic acid

Formula and Structure of Acrylic Acid
IUPAC name
Prop-2-Enoic Acid
CAS number
79-10-7
Commercial name
Propene Acid / Propenoic Acid
Other names
Acrylic Acid
Molecular formula
C3H4O2
Classification
Hydrocarbon
Molecular Structure
1.2
Brief History
Acrylic acid was first prepared in 1847 by air oxidation of acrolein, but it was not until 1914,
when Reppe discovered its synthesis from acetylene and CO in the presence of Ni compounds,
that it gained importance in the chemical industry. Interestingly enough, even after synthesizing
other routes of manufacturing, the original method involving oxidation of acrolein is still the
most favored industrial process for the manufacture of acrylic acid [3].
Acrylic acid is used primarily as a starting material in the synthesis of emulsion and solution
polymers. Acrylic emulsion polymers were first used as coatings for leather in the early 1930s
and have found wide utility as coatings, finishes and binders of leather, textiles and paper; as
exterior and interior coatings in home and industry; and as adhesives, laminates, elastomers,
plasticizers, and floor polishes [3].
1.3
Uses and Applications
Acrylic acid is used in the production of esters, polymers and specialty products. The chemicals
produced using acrylic acid, are primarily used as reactive building blocks to produce
polymers, coatings and inks, adhesives, sealants, textiles, plastics and elastomers.
Acrylic acid is mainly and globally used as an intermediate product to produce other end
products, such these products are polymers and acrylic ester. Acrylic esters made from acrylic
acid are ethyl acrylate, butyl acrylate, methyl acrylate, ethyl hexyl acrylate [4].
The end use pattern of acrylic acid in the year 2004 is listed in Table 1.2 with the percent cut
specified for each product.
Table 1.2 End use pattern of acrylic acid in the year 2014 [5]
End Use
Percent %
Acrylate Esters (56%)
n-Butyl acrylate
29
Ethyl acrylate
16
2-Ethylhexyl acrylates
Methyl acrylates
Specialty acrylates
5
Polyacrylic Acid and Salt (41%)
Superabsorbent polymers
32
Detergents
Water treatment and dispersants
Miscellaneous (3%)
Acrylic acid is usually not sold for direct consumer use, but it is used as a raw material to make
a variety of goods used by consumers or construction personnel and could be present in trace
amounts as residual monomer in consumer products [6].
The applications of acrylic acid and its derivatives are listed in Table 1.3.
Table 1.3 Fields of the application of acrylic acid and its derivatives [7]
Derivative Type
Application
Surface coatings
Adhesives and sealants
Plastic additives
Detergents
Acrylic Esters
Textiles
Resin modifiers
Yield-improving agents
Thermosetting coatings
Diapers and training Pants
Adult incontinence and other personal care products
Acrylic Polymers
Water treatment (dispersants, anti-scalants, thickeners)
and
Mineral processing
Other Derivatives
Detergent co-builders
Soaker pads used in food packaging
Washing powder formulations
1.4
Physical and Chemical Properties of Acrylic Acid
1.4.1 Physical Properties

Acrylic acid is a colorless liquid with an irritating acrid odor at room temperature and pressure.
Its odor threshold is low (0.20-3.14 mg/m3). It is miscible in water and most organic solvents.
It freezes at 13-14 C and boils at 141 C [4].
A list of the fundamental physical properties is given in Table 1.4. For more detailed physical
data of Acrylic Acid, readers are advised to refer to the Material Safety Data Sheet (MSDS)
given in Appendix 1.
Table 1.4 Physical properties of acrylic acid [4]

Physical Properties
Physical state at 15 C and 1 atm
Liquid
Molecular weight
72.06 (g/mole)
Color
Colorless
Odor
Acrid, pungent
Solubility
Cold water, slightly in acetone
Freezing point
13 - 14 (C)
Boiling point
141 (C)
Vapor pressure
3 (mmHg)
Thermal conductivity
0.159 (W/m/K) at 20 C
0.136 (W/m/K) at 100 C

Density
1.05 g/mL at 20 C
1.04 g/mL at 30 C
Viscosity
1.19 cP at 20 C
0.85 cP at 40 C
0.73 cP at 50 C
1.4.2 Chemical and Thermodynamic Properties

Acrylic acid undergo reactions characteristic of both unsaturated acids and aliphatic carbolic
acid or esters. The high reactivity of these compounds stems from the two unsaturated centers
situated in the conjugated position.
The carbon atom polarized by carbonyl group, behaves as an electrophile; this fovours the
addition of large variety of nucleophiles and active hydrogen compounds to the vinyl group.
Moreover, the carbon-carbon double bond undergoes radical-initiated addition reactions,
Diels-Alder reactions with dienes, and polymerization reactions [8].
Acrylic acid goas under polymerization reaction with methacrylic acid in the presence of light,
heat and oxygen, and also under the action of oxidizing agents such as peroxides [8]. These
materials are capable of thermally induced or chemically initiated radical type polymerization
reactions which can generate significant amounts of heat [9].
Thermodynamic and chemical properties are essential for process design calculations. Table
1.5 lists a number of thermodynamic and chemical properties. These properties include the heat
of vaporization at 27 C and heat of combustion at 25 C which are 27.8 and 1376 kJ/mol
respectively.
Table 1.5 Chemical and thermodynamic properties of acrylic acid [4]
Chemical and Thermodynamic Properties
Henry's law constant at 25 C
3.7 10-7 atm-cu m/mol
Critical temperature
342 (C)
Critical pressure
56 (atm)
Heat of vaporization at 27 C
27.8 (kJ/mol)
Heat of combustion at 25 C
1376 (kJ/mol)
Heat of fusion
11.1 (kJ/mol)
Heat of polymerization
77.5 (kJ/mol)
Heat of neutralization
58.2 (kJ/mol)
Specific heat at 25 C
2.09 (kJ/kg/K)
Dissociation constant at 25 C
5.5 10-5
Antoine equation constants

A = 2.69607
B = 621.275
C = -121.929
1.4.3 Safety and Toxicological Properties

Regarding the hazardous prospective to the acrylic acid, a list of safety and toxicological
properties are listed in Tables 1.6 and 1.7, respectively, to give a general view on the toxicity
and safety procedures must be taken for the acrylic acid handling and manufacturing.
Acrylic acid is a flammable volatile liquid with an auto ignition temperature of 412 C. It has
lower and upper flammable limits of 2.4 and 8.0 volume%, respectively, in air. Moreover,
acrylic acid is considered toxic and harms the lungs, nervous system and mucous membranes.
It enters the body by dermal and eye contact, inhalation and ingestion.
Table 1.6 Safety properties of acrylic acid [8]

Safety Properties
Fire potential
Flammable liquid
Auto-ignition temperature
412 (C)
Flash point temperature (C)
Closed cup (50 C), Open cup (54 C)
Products of combustion
(CO), (CO2) and (H2O)
Flammable limits in air (Volume %)

Lower = 2.4
Upper = 8.0
Table 1.7 Toxicological properties of acrylic acid [10]

Toxicological Properties
TLV
2 ppm (5.9 mg/m3) TWA [skin]
PEL
10 ppm (for 8 hours)
REL
2 ppm (6.0 mg/m3) TWA [skin]
LD50
340 mg/kg
PEL: Permissible Exposure Limit (by OSHA) is for General and Construction industry and maritime. TLV: Threshold Limit
Value (ACGIH). REL: Recommended Exposure Limit (NIOSH)
1.5
Market Analysis
1.5.1 Overview
Increasing population, increasing lifespan, and improving lifestyle have all significantly
increased the demand and growth of super absorbent polymers market in the developed and
developing world which includes disposable hygiene products.
The majority of the market growth is projected to occur in China and India as these countries
produce increasing amounts of products using acrylic acid as intermediates with applications
including detergents, coatings, adhesives, sealants, as well as personal care items [11].
As feedstock costs continue to increase and downstream demand remains flat, the global acrylic
acid market is expected to face challenges in the coming years. Production costs for acrylic
acid are expected to continue increasing.
Acrylic acid plants may face a number of competitive challenges from renewable acrylic
acid pathways. The selling price of acrylic acid is expected to drop if bio acrylic acid
plants are able to scale-up their process to industrial production levels [12].
Many major companies are competing in the acrylic acid market (see Table 1.8). SAMCO is
located in Saudi Arabia and has one of the largest complexes in the world. The acrylic acid
plant at SAMCO has a production capacity of 160,000 tons annually [13].
Table 1.8 Acrylic acid major manufacturers [13]
Company
Location
SAMCO
Saudi Arabia
Dow Chemical
United States
CNOOC
China
Jiangsu Jurong
China
Shanghai Huayi Acrylic Acid
China
Sanmu Group
China
Arkema
France
BASF
Germany
FPC
Taiwan
BASF
Brazil
SC Gazprom Neftekhim
Russia
Mitsubishi Chemical Corporation
Japan
Nippon Shokubai
Japan
LG Chem
South Korea
1.5.2 Worldwide Production of Acrylic Acid

After a decline in 2009, the global acrylic acid market returned to stable growth; the overall
acrylic acid output grew by around 4.5% annually in 2010 and 2011 [14]. In 2012, the world
acrylic acid supply registered a 4.7% year over year increase and touched the 4.7 million tons
mark [2].
Asia-Pacific ranks the regions leading acrylic acid producer; with China capturing around
28.3% share of the overall supply volume. In 2012, China nearly doubled its acrylic acid supply
volume if compared to 2007, and the countrys production is poised to follow a stable upward
trend in the upcoming years. The US, Germany, Japan and South Korea are yet other major
acrylic acid manufacturers worldwide [14]. The acrylate esters industry is the major acrylic
acid end-user, which consumed over half of the total annual production in 2012 [6].
The worldwide acrylic acid production volume is poised to witness sustained growth in the
years ahead, driven primarily by the increasing demand from the end-use industries as well as
planned capacity additions. In 2017, the global acrylic acid production is anticipated to climb
to 5.94 million tons [14].
1.5.3 Worldwide Consumption of Acrylic Acid

In the year 2012, the European market was the largest consumer for acrylic acid derivatives in
2012, whereas, North American market was the largest consumer of acrylic acid in 2012. The
demand trend for acrylic acid and its derivatives is expected to increase gradually in AsiaPacific until 2018 [15].
Figure 1.1 shows the global demand (consumption) in 2012 and the expected global demand
in 2016.
Figure 1.1 Global demand of acrylic acid in 2012 and 2016 (expected) [16]
1.5.4 Prices of Acrylic Acid and Its Raw Materials

Figure 1.2 shows the prices of acrylic acid and propylene for the period from 2000 to 2012.
One can notice from the figure that the prices of acrylic acid and propylene were almost the
same from the period 2000 to 2006. The figure shows a reasonable increase in prices to reach
2250 and 1700 USD/MT for acrylic acid and propylene, respectively.
The prices kept fluctuating from the end of 2000 to early 2008. At the end of 2008, propylene
experienced a severe collapse in its price to below 700 USD/MT due to worlds financial crisis.
At the successive years, the prices kept increasing until they reached 2400 and 1350USD/MT
for acrylic acid and propylene, respectively.
Figure 1.2 Acrylic acid and propylene prices in 2000 2012 [13]
10
C h a p t e r Tw o : P r o d u c t i o n P r o c e s s e s a n d P r o c e s s S e l e c t i o n
CHAPTER TWO
Production Processes and Process Selection
2.1
2.1.1 Background
An important route to acrylic acid is the vapor phase oxidation of propylene over a
multicomponent catalyst containing molybdenum and/or other metals, usually as their oxides.
Typically, this is carried out in two steps. The first reaction step involves oxidation of propylene
with air (oxygen) to form acrolein, often with a minor amount of acrylic acid, along with carbon
oxides, water and smaller amounts of other oxidized byproducts. The second reaction step then
converts acrolein to acrylic acid by a similar oxidation step, but typically using different
reaction conditions and catalyst for optimum results [17].
The reaction is the conversion of propylene to acrylic acid through the use of a catalyst
C3H6 + 1.5 O2 C3H4O2 + H2O
(2.1)
Two side reactions are involved in the process

C3H6 + 2.5 O2 C2H4O2 + CO2 + H2O
(2.2)
C3H6 + 4.5 O2 3 CO2 + 3 H2O
(2.3)
The first competing reaction produces a sellable commodity, acetic acid, while the second only
produces purge gases [18]. Fortunately, kinetics are favorable for the desired product, acrylic
acid, and the secondary product, acetic acid.
11
2.1.2 Reactor
Typically these reactions are carried out in multitubular fixed-bed reactors. The large
exothermic heat of reaction and the thermal sensitivity of the propylene oxidation requires low
feed concentrations, expensive heat transfer equipment, and good reactor temperature control.
Low propylene concentration is also required to avoid flammability conditions [19].
The magnitude of some of these problems is reduced when fluidized-bed reactors are used. The
temperature can be readily controlled within a few degrees because of the intensive catalyst
mixing and the good heat transfer characteristics [17].
2.1.3 Catalyst
While specifics are not widely published, it is known that when the reaction is taking place
over a single stage catalyst, polyvalent metal oxides are used. In particular, molybdenum as a
component and tellurium as an aid to product selectivity can be utilized. However, due to
activity loss at a higher rate in tellurium, this in not feasible in large-scale production [18].
More common is the use of two separate catalysts, one to propel each of the oxidation steps:
from propylene to acrolein and from acrolein to acrylic acid [18]. Based on one article, these
catalysts can last in upwards of 3 years, making them highly effective for plant use. In
particular, the oxidation of propylene activates over a mixture of metallic oxides. These include
Mn2O3, V2O5, and MoO3 ground together and then calcinated at high temperatures [19].
2.2
Production of Acrylic Acid from Propane
2.2.1 Background
Acrylic acid can also be produced through a one-step selective oxidation of propane over a
selective catalyst according to the following reaction
C3H8 + 2.0 O2 C3H4O2 + 2.0 H2O
(2.4)
Side reactions of this process include total oxidation, as seen in reactions (2.5) to (2.7) and the
production of acetic acid through activated propylene or acrolein, as seen in reaction (2.8).The
total oxidation side reactions can be minimized by maintaining the reactor temperature at the
desired level by removing excess heat from the highly exothermic reaction [20].
12
The use of an inert gas, such as water or nitrogen, may prevent excess oxidation of propylene
by enhancing the desorption of acrylic and acetic acids from the catalyst surface [12].
C3H8 + 5.0 O2 3.0 CO2 + 4.0 H2O
(2.5)
C3H6 + 4.5 O2 3.0 CO2 + 3.0 H2O
(2.6)
C2H4O2 + 2.0 O2 2.0 CO2 + 2.0 H2O
(2.7)
C2H4O + 1.5 O2 CO2 + C2H4O2
(2.8)
2.2.2 Reactor
The process is operated with multiple reactors so that frequent regeneration is possible. The
details of such operations are complicated and will not be considered here. The reactors
typically will be of the tubular type [21].
2.2.3 Catalyst
Propane partial oxidation to acrylic acid over vanadium pyrophosphate (VPO) catalysts,
heteropolyacids, and multi-component oxidic catalysts has been studied in great depth. Only
recently has a catalyst system been developed that is active and selective enough to substitute
for the existing industrial process. This is due to the difficulty in maintaining high reaction
temperatures (so the reaction rate will be high) while preventing total oxidation reactions [20].
2.3
Production of Acrylic Acid from Acetylene
2.3.1 Background
It is well known that acrylic acid and its esters can be produced by the reaction of acetylene
and carbon monoxide with compounds having a replaceable hydrogen, such as water, alcohols,
carboxylic acids, ammonia and amines. This is probably the oldest method of producing acrylic
acid. Acetylene, reacts with CO and water to produce acrylic acid according to the following
reaction
C2H2 + CO + H2O C3H4O2
13
(2.9)
2.3.2 Reactor
The reaction can be carried out in a batch or continuous flow reactor [22]. The acetylene and
carbon monoxide can be added separately, or safety reasons, as a mixture of gases.
2.3.3 Catalyst
The reaction takes place in the presence of a metal carbonyl catalyst, or other catalysts such as
the complex triphenylphosphine-nickel halide compounds or the complex nickel halidequarternary ammonium compounds [23]. The catalyst complexes suitable for use in this
process are prepared by admixing a nickel halide, such as nickel bromide, nickel chloride,
nickel fluoride or nickel iodide, with one or more of the aliphatic amines [22].
In preparing the catalyst complex, the order of addition of the two components is not critical.
Thus, the aliphatic amine can be added initially to the alcohol reactant to be used in producing
the acrylic acid ester, followed by the nickel halide component, or the reverse order of addition
can be followed [22]. The acrylic acid esters are then produced by the interaction of acetylene
with carbon monoxide and the alcohol at elevated temperature and under increased pressure in
the presence of a catalytic amount of the catalyst complex [13].
2.4
Process Selection
The advantages and disadvantages for each process discussed thus far are presented here. The
purpose of this section is to provide a basis for the evaluation of the best production process to
make design calculations (chapter five). The evaluation mechanism is based on the multiplecriteria decision analysis method, given in Table 2.1. The process with the highest number of
points will be selected accordingly.
Acrylic Acid from Propylene
Advantages
Increased capacity is provided without additional capital expenditure
Reduction in the waste generated by the process
Less energy is required due to the reduced compressor load
Uses the least expensive reactants compared to other alternatives
Interstage problems are substantially eliminated
Lower pressure drop in the reactor due to the increased feed composition
14
Catalyst is regenerable
Catalyst is relatively non-toxic and non-corrosive
Produces less pollution on a mass bases
Increased selectivity
Disadvantages
Large loss of raw material (propylene) due to purging
Catalyst deactivates when operated above 370 C
Acrylic Acid from Propane
Advantages
Limitation of the over-oxidation of the products formed
Increased acrylic acid selectivity
Conversion is increased without loss of selectivity
Catalyst is relatively non-toxic and non-corrosive
Disadvantages
Large loss of raw material (propane) due to purging
The reaction has to take place in two reactors operating at different conditions
Costs more than the propylene pathway
Acrylic Acid from Acetylene
Advantages
Disadvantages
Costs more than the propylene pathway
Uses commodity reactant (more expensive than chemical reactants)
Catalyst is highly toxic and corrosive
Catalyst is expensive to purchase and even more expensive to dispose of
Produces extremely toxic and hard to recover by-products
Uses highly corrosive reactants
Reaction mechanism is not yet understood
15
Table 2.1 Multiple-criteria decision analysis for selecting the best method
Criteria
Weight
Propylene
Propane
Acetylene
Cost
100
100
80
50
Selectivity
80
78
80
70
Yield
80
78
80
70
Catalyst regenerability
80
80
80
70
Toxicity
70
70
70
30
Treatment of purge
60
60
55
40
Maintenance
60
60
55
50
Feed pretreatment
50
50
50
45
Total
580
576
550
425
Table 2.1 shows that production of acrylic acid from propylene is, as far as we are concerned,
the best production process of acrylic acid. This is evident from the fact that it gained the
highest number of points, 576/580, compared to 550/580 for production from propane and
425/580 for production from acetylene.
As mentioned previously, the information given in Table 2.1 is based on the advantages and
disadvantages discussed previously. It should be noted that the cost criterion is assigned the
highest number of points, which means that it is the most important aspect of selection, or at
least from our own perspective. Note that for a certain criterion, the process with the best
performance in that region is automatically assigned full points, and the remaining processes
are compared accordingly.
The flowsheet and mass balance calculations for the propylene process are given in Figure 2.1
and Table 2.2, respectively. These have been provided by Eng. Ashraf Yousef. It is seen that
the main product stream (18) has a molar flowrate of 156.24 kmol/h. This corresponds
AA produced = 156.24
kmol 72 kg 24 hours 330 days
= 98543692.8 kg/year
hour 1 kmol
1 day
1 year
Note that 330 days/year is used since it is assumed that the plant shuts down for 35 days/year
for maintenance.
16
Chapter Two: Pr oduc tion Processes and Pr ocess Selection
Figure 2.1 Production of acrylic acid from propylene process flowsheet
17
Chapter Two: Pr oduc tion Processes and Pr ocess Selection
Table 2.2 Production of acrylic acid from propylene mass balance sheet
Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Vapor Frac
Propylene
Nitrogen
Oxygen
CO2
Water
Acrylic
Acetic
25.00
1.00
1.00
0.00
1902.06
505.62
0.00
45.54
0.00
0.00
159.00
6.00
1.00
0.00
0.00
0.00
0.00
1786.14
0.00
0.00
25.00
11.50
1.00
228.60
0.00
0.00
0.00
0.00
0.00
0.00
191.00
4.30
1.00
228.60
1902.06
505.62
0.00
1831.68
0.00
0.00
310.00
3.50
1.00
26.46
1902.06
93.42
108.90
2098.62
11.77
158.02
63.00
2.00
0.00
0.00
0.00
0.00
0.00
253.62
1.17
12.58
40.00
2.40
0.00
0.00
0.00
0.00
0.00
141966.00
747.00
10647.00
40.00
1.00
1.00
26.46
1902.06
93.42
108.90
270.18
2.00
14.35
10
50.00
2.40
0.00
0.00
0.00
0.00
0.00
144048.06
757.98
10803.24
11
48.00
1.00
1.00
26.46
1902.06
93.42
108.90
270.36
0.83
1.76
12
25.00
5.00
0.00
0.00
0.00
0.00
0.00
253.80
0.00
0.00
14
102.00
1.10
0.00
0.00
0.00
0.00
0.00
2081.52
0.05
0.00
15
90.00
0.19
0.00
0.00
0.00
0.00
0.00
0.54
10.94
156.26
16
47.00
0.07
1.00
0.00
0.00
0.00
0.00
17.01
341.82
0.56
17
47.00
1.10
0.00
0.00
0.00
0.00
0.00
0.54
10.85
0.02
18
40.00
2.50
0.00
0.00
0.00
0.00
0.00
0.00
0.09
156.24
18
Ch a p te r Th r e e : Sa fe t y Im pa c ts a n d E n vi r o nme n ta l S tu d y
CHAPTER THREE
Safety Impacts and Environmental Study
3.1
Introduction
Safety considerations are paramount in the chemical industry and should not be left out of the
project. This topic gives the reader an intuition of the safety-related aspects that influence the
plant design and/or plant workers. The study of environmental impacts and safety is dependent
on investigating previous accidents/incidents, identifying whether a material is combustible,
flammable, or toxic, and formulating measures to reduce potential hazard consequences. The
environmental impacts and safety issues are usually concerned with the chemicals that are
involved in the process as a raw, intermediate, or product materials.
This chapter is intended to provide essential information that should assist personnel who work
with acrylic acid to avoid dangerous conditions. Prevention features should be a key part of the
design and operation of acrylic acid storage facilities.
3.2
Instability of Acrylic Acid
Acrylic acid will readily polymerize if not properly inhibited. Uncontrolled polymerization is
rapid and can be very violent, generating large amounts of heat which increases the pressure.
This increase in pressure causes the ejection of hot vapor and polymer which may autoignite.
Explosions have been caused by uncontrolled polymerization of acrylic acid [24].
Several case histories of acrylic acid explosions were reported when procedures for proper
handling or storage were disregarded [25]. Depending on the conditions, the polymerization
can proceed with moderate speed associated by a slow temperature increase, or it could become
violent under unfavorable conditions. Explosion hazards exist, if polymerizing material is
enclosed in a poorly vented or unvented container. Pressure build-up may occur rapidly and
can lead to the rupture of pipelines, vessels and other containers.
19
3.3
Health and Safety Factors
3.3.1 Toxicity
Absorption of acrylic acid can occur through the skin or lung after dermal or inhalation
exposure. It is rapidly metabolized by normal oxidative catabolic pathways and is eliminated
mainly as expired carbon dioxide [26]. Acrylic acid causes severe burns to skin and eyes and
severe irritation in the respiratory tract.
3.3.2 Industrial Hygiene

Industrial hygiene involves the recognition, evaluation, and control of workplace health
hazards. When Acrylic acid is used in the workplace, it is important to evaluate the conditions
of use (where, how, how often), to determine the potential for employee exposure [27]. Since
acrylic acid can be inhaled, ingested, or absorbed through the skin, each of these potential
routes of exposure must be assessed and managed appropriately.
Inhalation of Acrylic acid can occur when conditions cause the material to become airborne.
Concentrations of acrylic acid in the air can be determined through air sampling and analysis.
Air sampling results are compared to the workplace exposure limit in order to determine the
need for ventilation or respiratory protection.
3.3.3 Medical Management

Medical management should establish procedures to be followed if an exposure incident
occurs. An important issue to be considered is the medical approval to work with a respiratory
mask. Since the use of respiratory protection may be required in the work area, respiratory
fitness must be evaluated regularly to determine the employees ability to wear a respirator.
The use of contact lenses, in areas where acrylic acid is handled even wearing goggles, should
be carefully evaluated.
3.3.4 First Aid

When providing first aid to a person who has been exposed to acrylic acid, the person should
be removed from the area to prevent further exposure. The type of exposure the person has
experienced should be determined by eye or skin contact, inhalation or ingestion. The persons
contaminated clothes must be removed [24].
20
In case of eye exposure to acrylic acid at any concentration, the person should immediately go
to the nearest eyewash station and flush his/her eyes with water for at least 15 minutes while
holding eyelids open and away from the eyes [28]. A physician should be contacted
immediately for further medical attention.
If acrylic acid comes in contact with a persons skin or clothing, the individual should
immediately go to the nearest safety shower and rinse off the acrylic acid. The affected area(s)
of the person should be washed continuously with large quantities of water for at least 15
minutes or longer if odor persists.
Personnel affected by acrylic acid vapors must be moved to a well-ventilated area. If an
individual is not breathing, administer artificial respiration [29]. Obtain a physicians assistance
or that of another trained emergency health professional as soon as possible and transport to a
clinic or hospital. If breathing is difficult, trained personnel should administer oxygen.
3.4
Personal Protective Equipment
Personal protective equipment are available in a variety of sizes. Improperly sized and
uncomfortable equipment may compromise its effectiveness and create additional safety
hazards. Personal protective equipment should be selected on the basis of potential exposure
via a job safety analysis. Several of these equipment are listed in Table 3.1.
Table 3.2 Examples of personal protective equipment [25]
Protected Area
Equipment
Splash goggles
Eye
Contact lenses
Face shield
Chemical resistant gloves
Full body overalls
Skin
Rubber boots
Face shields
Air purifying respirators
Respiratory
Air supply respirators
21
3.5
Storage of Acrylic Acid
The recommended storage temperature is 15 25 C. The lower limit of 15 C is intended to

provide a reasonable safety margin from the freezing point of 13 C. The upper limit of 25 C
has been identified to reduce diacrylic acid formation [25].
Adequate inhibition is necessary to avoid polymerization when storing acrylic acid. The
standard inhibitor concentration of commercial acrylic acid is approximately 200 ppm MeHQ.
Phenolic inhibitors (stabilizers) like MeHQ require the presence of dissolved oxygen for
stabilizing effect [30].
Critical conditions are typically detected by a temperature increase. A minimum of two
independent temperature probes is recommended for storage tanks. The temperature probes
should be located in the liquid phase near the bottom of the vessel. The temperature signal
should be recorded and monitored continuously in the control room [30]. An inexplicable
temperature increase could be an early warning sign of potentially unsafe conditions.
3.6
Transport and Loading/Uploading
Acrylic acid must be transported and handled under an atmosphere containing at least 5%
oxygen. The MeHQ stabilizer is not effective in the absence of oxygen. Pure nitrogen or other
oxygen-free gases will reduce the amount of dissolved oxygen, resulting in a hazardous
situation. The transport vessel has to be made of stainless steel and insulated in order to
maintain the product temperature between 15 and 25 C [24].
It is recommended that only acrylic acid be loaded in the compartments of the vessel. In case
of combination load deliveries, the compartments next to the one containing acrylic acid should
remain empty and sealed. Definitely, only compatible materials should be included in the
combination load.
The contents of the vessel must be positively identified before they are transferred. Sampling
and analysis are considered as appropriate measures for product identification. Continuous
monitoring of the unloading process is recommended. Acrylic acid should be unloaded using
a vapor return line in order to limit emissions to the environment. The vapor return line is
recommended to be a standard connector.
22
3.7
Environmental Considerations
3.7.1 Waste Disposal

Saudi regulations governing waste disposal make it essential for producers, suppliers and users
of acrylic acid to be fully aware of viable options for the ultimate disposal of materials
containing acrylic acid. Materials to be disposed of may be residues from production or
cleaning operations as well as waste material from spills.
Wastes of the monomer may be diluted and washed into a biological waste water treatment
plant after notification of the person in charge. The biodegradability of the material in diluted
form is good. However, acrylic acid may be toxic to the system if the bacteria have not been
conditioned properly to this material. Accordingly, the initial feed rate should be low with a
stepwise increase [25].
Solid materials containing acrylic acid, such as absorbents or polymeric material can be
disposed of by incineration [31]. Disposal in landfills must be thoroughly checked with the
authorities and should be practiced only as a last resort. For disposing of waste materials
originating from laboratory or retain samples, great care must be exercised to keep the
monomer separated from incompatible materials (see Appendix 2, Incompatible Materials),
which may initiate polymerization.
3.7.2 Air Emissions

Discharges of acrylic acid vapors into the atmosphere are subject to restrictions in Saudi
Arabia, and must therefore be disposed of in conformity with air pollution control regulations.
The most appropriate way is to avoid emissions resulting from displaced gases, if possible. In
most cases this can be accomplished by back venting through a vapor return line [24]. The use
of venting pipes, however, must effectively exclude contamination of the acrylic acid. Vapor
return lines must be heat traced to avoid condensation of acrylic acid vapors which do not
contain any stabilizer.
Exhaust gases loaded with acrylic acid originating from production should be cleaned prior to
being emitted into the atmosphere [26]. The exhaust gas can be treated via a thermal
combustion unit, e.g. flare, catalytic conversion unit, or caustic scrubber.
23
3.8
Production of Acrylic Acid by Propylene
We have only considered general environmental and safety considerations for handling acrylic
acid thus far. This section is devoted entirely to discussing safety procedures and environmental
impacts for all the components involved in the production process of acrylic acid by propylene.
3.8.1 Maximum Allowable Exposure Limits

Four output streams are shown in the process flowsheet (see Figure 2.1). Streams 11 and 14
are waste streams while streams 17 and 18 are product streams. Waste stream 14 will not be
considered here since it contains water steam and hence can be readily disposed of. Stream 11,
however, contains toxic substances and is therefore the topic of concern in this context.
Discharge of these toxic chemicals are subjected to restrictions that are imposed by local and
international standards. Therefore, no release of any chemicals as an air emission will be
allowed without a permit from either the Royal Commission for Jubail and Yanbu (RCJY) or
the Presidency of Meteorology and Environment (PME). Consequently, the measurement of
the concentrations of stream 11 is essential in complying with these regulations.
Flowrates and molar compositions for the components comprising stream 11 are listed in Table
3.2. Nitrogen, oxygen, and water steam are considered environment-friendly and hence no
further study of their emission levels is needed. However, propylene, carbon dioxide, acrylic
acid, and acetic acid are considered toxic (to some extent) and will be investigated accordingly.
Maximum exposure limits for these four components are listed in Table 3.3.
Table 3.3 Flowrates and molar compositions of stream 11
Component
Temp (K)
Pressure (bar)
Flow (kmol/hr)
Composition
Propylene
321.15
1.00
26.460
0.011
Nitrogen
321.15
1.00
1902.060
0.791
Oxygen
321.15
1.00
93.420
0.039
Carbon dioxide
321.15
1.00
108.900
0.045
Water
321.15
1.00
270.360
0.112
Acetic Acid
321.15
1.00
0.830
0.000
Acrylic Acid
321.15
1.00
1.760
0.001
Total
321.15
1.00
2403.790
1.000
24
Table 3.4 Maximum allowable exposure limits [32]

TLV
PEL
REL
MAK
Component
ppm
mg/m3
ppm
mg/m3
ppm
mg/m3
ppm
mg/m3
Propylene
500
CO2
5000
9000
5000
9000
5000
9000
5000
9000
Acetic Acid
10
25
10
25
10
25
10
25
Acrylic Acid
5.9
TLV: Threshold Limit Value (ACGIH). PEL: Permissible Exposure Limit (by OSHA) is for General and Construction
industry and maritime. REL: Recommended Exposure Limit (NIOSH). MAK: Maximum Workplace Concentration.
In case of exceeding the permitted emission concentration of these components to air, the use
of treatment units is required.
3.8.2 Toxicology / Health Effects / Handling / Personal Protection

Table 3.4 contains safety data (toxicology, health effects, handling, and protection) for all the
components involved in the production process.
Table 3.5 Safety data for all the components involved in the production process [11 20]
Propylene
Propylene is nontoxic but can act as a simple asphyxiant by displacing
Toxicology
oxygen.
May cause suffocation by displacing the oxygen in the air. Exposure
to oxygen deficient atmosphere (<19.5%) may cause dizziness,
drowsiness, vomiting, excess salivation, diminished mental alertness,
Health Effects
loss of consciousness and death. Exposure to atmospheres containing

8-10% or less oxygen will bring about unconsciousness without
warning and so quickly that the individuals cannot help or protect
themselves.
Propylene is stored as a refrigerated liquid at -47C and transported by
refrigerated vessels. Tanks and pipes should be made of stainless steel
Transport/Handling
or nickel alloys with suitable insulation. It can be transported by tank

trucks in the same manner as LPG.
25
Commented [HA5]: fix
Wear protective eyewear (safety glasses). Work gloves and safety

shoes are recommended when handling cylinders. Cotton clothing is
recommended to prevent static build-up. If exposure limits are
exceeded or irritation is experienced, NIOSH/MSHA approved
respiratory protection should be worn. Positive-pressure supplied air
Personal Protection
respirators may be required for high airborne contaminant

concentrations. Respiratory protection must be provided in accordance
with current local regulations. Use positive pressure airline respirator
with escape cylinder or self-contained breathing apparatus for oxygendeficient atmospheres (<19.5%).
Nitrogen
In-adequate evidence for humans and animals. Generally speaking,
Toxicology
nitrogen is nontoxic but can act as a simple asphyxiant by displacing

oxygen.
Simple asphyxiant. May cause suffocation by displacing the oxygen
Health Effects
in the air.
Use only in ventilated areas. Protect cylinders from physical damage;
do not drag, roll, slide or drop. When moving cylinders, even for short
distance, use a cart designed to transport cylinders. Use equipment
rated for cylinder pressure. Use backflow preventive device in piping.
Transport/Handling
Never insert an object (e.g. wrench, screwdriver, pry bar, etc.) into
valve cap openings. Doing so may damage valve, causing leak to
occur. Never put cylinders into trunks of cars or unventilated areas of
passenger vehicles.
Work gloves and safety shoes are recommended when handling
cylinders. Use positive pressure airline respirator with escape cylinder
Personal Protection
or
self-contained
breathing
atmospheres (<19.5%).
26
apparatus
for
oxygen-deficient
Oxygen
Human volunteers which inhaled 90-95% oxygen through a face mask
for 6 hours showed signs of tracheal irritation and fatigue. Other
symptoms (which may have been caused by placing a tube into the
Toxicology
trachea during the experiment) included: sinusitis, conjunctivitis,

fever, and symptoms of acute bronchitis. Poisoning began in dogs 36
hours after inhalation of pure oxygen at atmospheric pressure. Distress
was seen within 48 hours and death within 60 hours.
Oxygen is not acutely toxic under normal pressure. Oxygen is more
toxic when inhaled at elevated pressures. Depending upon pressure
Health Effects
and duration of exposure, pure oxygen at elevated pressures may cause

cramps, dizziness, difficulty breathing, convulsions, edema and death.
Moisture causes metal oxides which are formed with air to be hydrated
so that they include volume and lose their protective role (rust
formation). Concentrations of SO2, Cl2, salt, etc. in the moisture
enhances the rusting of metals in air. Carbon steels and low alloy steels
Transport/Handling
are acceptable for use at lower pressures. For high pressure

applications stainless steels are acceptable as are copper and its alloys,
nickel and its alloys, brass bronze, silicon alloys, and beryllium.
Protect from physical damage.
Work gloves and safety shoes are recommended when handling
Personal Protection
cylinders. Gloves must be clean and free from grease or oil.

Carbon Dioxide
Carbon dioxide (CO2) is a toxic gas at high concentration, as well as
Toxicology
an asphyxiant gas (due to reduction in oxygen). Irritation of the eyes,

nose and throat occurs only at high concentrations.
Concentrations of 10% CO2 or more can produce unconsciousness or
Health Effects
death. In high concentrations may cause asphyxiation. Victim may not

be aware of asphyxiation.
27
Self-contained breathing apparatus (SCBA) or positive pressure

airline with mask are to be used in oxygen-deficient atmosphere. Air
Personal Protection
purifying respirators will not provide protection. Users of breathing

apparatus must be trained.
Water
Water is nontoxic but can act as a simple asphyxiant by displacing
Toxicology
Health Effects
Personal Protection
oxygen.
None.
Use heat protective garment when exposed to large quantities of

heated vapor.
Acetic Acid
Extremely hazardous in case of inhalation (lung corrosive). Very
hazardous in case of skin contact (irritant), and of ingestion.
Toxicology
Hazardous in case of skin contact (corrosive, permeator), and of eye

contact (corrosive).
Very hazardous in case of skin contact (irritant), of eye contact
(irritant), of ingestion, and of inhalation. Skin contact may produce
Health Effects
burns. Inhalation of the spray mist may produce severe irritation of

respiratory tract, characterized by coughing, choking, or shortness of
breath.
Keep away from sources of ignition. Ground all equipment containing
material. Never add water to this product. In case of insufficient
ventilation, wear suitable respiratory equipment. If ingested, seek
Transport/Handling medical advice immediately and show the container or the label.
Avoid contact with skin and eyes. Keep away from incompatibles such
as oxidizing agents, reducing agents, metals, acids, alkalis. Store in a
segregated and approved area.
28
Splash goggles. Full suit. Vapor respirator. Boots. Gloves. A selfPersonal Protection contained breathing apparatus should be used to avoid inhalation of
the product. Suggested protective clothing might not be sufficient.
Acrylic Acid
Acrylic acid is considered slightly toxic to animals by inhalation.
Animal exposure studies have not indicated that acrylic acid poses a
Toxicology
cancer hazard. Acrylic acid did not cause birth defects in laboratory
animals and showed no reproduction effects at doses that were not
significantly toxic to the parent animals.
Very hazardous in case of skin contact (permeator), of eye contact
(irritant, corrosive). Corrosive to skin and eyes on contact. Spray mist
may produce tissue damage particularly on mucous membranes of
eyes, mouth and respiratory tract. Skin contact may produce burns.
Health Effects
Inhalation of the spray mist may produce severe irritation of

respiratory tract, characterized by coughing, choking, or shortness of
breath. Severe over-exposure can result in death. Inflammation of the
eye is characterized by redness, watering, and itching.
Use explosion-proof equipment. Polymerization is a highly
exothermic reaction and may generate sufficient heat to cause thermal
Transport/Handling decomposition and/or rupture containers. Keep containers tightly

closed in a dry, cool and well-ventilated place. The stabilizer is only
effective in the presence of oxygen. Keep away from heat.
Keep containers tightly closed in a dry, cool and well-ventilated place.
The stabilizer is only effective in the presence of oxygen. Keep away
Personal Protection
from heat. Do not breathe vapors or spray mist. Avoid contact with the
skin and the eyes. Wear suitable protective equipment.
29
3.9
Previous Incidents Involving Acrylic Acid Production
3.9.1 Nippon Shokubai Himeji Plant Incident

The site of the accident, Nippon Shokubais Himeji Plant, is a manufacturing plant with a site
area of about 900,000 m, situated in the southwest corner of the city of Himeji, Hyogo
Prefecture. The Himeji Plant produces basic chemicals (e.g. acrylic acid and acrylic esters),
functional chemicals (e.g. super absorbent polymers, electronic and information materials),
catalysts and other products [33].
At about 14:35 on September 29, 2012, an explosion occurred at the Nippon Shokubai Co.,
Ltd. Himeji Plant located in Himeji, Hyogo Prefecture, Japan. The explosion and subsequent
fire in an acrylic acid intermediate tank killed one person and injured 36 [34]. The acrylic acid
intermediate tank (V-3138), where the explosion and fire occurred, is located in an acrylic acid
production facility in the basic chemicals production yard, shown in Figure 3.1.
Figure 3.3 Overview of the Himeji Plant, Nippon Shokubai
30
The tank was installed in November 1985 [34]. It is used as an intermediate tank for temporarily
storing the withdrawal liquid from the rectifying column when, for example, the rectifying
column stopped. A schematic of this tank is shown in Figure 3.2.
Figure 3.4 Schematic of tank V-3138
The committee responsible for investigating the accident identified the causes as follows [34]:
i.
Acrylic acid remained stagnant for a long period of time at high temperature in the
upper portion of the tank.
ii.
DAA formation accelerated in the tank liquid with high temperature zones and the heat
of dimerization has caused the liquid temperature to increase. This has also caused
acrylic acid to polymerize and increase the temperature even further.
iii.
Due to lack of thermometers and inadequate temperature monitoring, it was not possible
to detect the abnormal condition until polymerization had proceeded.
These direct causes had resulted in the explosion of V-3138.
31
3.9.2 Yokohama Chemical Factory

On January 19, 1969, an explosion occurred on the first floor of a factory at a stainless steel
drum can of 200 L capacity holding acrylic acid. The lid of the drum can was blown off and a
gas explosion occurred with the ignition to the spouting gas in the air. The four-floor factory
building collapsed [35].
Five drum cans of acrylic acid, which were received about one month before, solidified because
of low temperature. For using the acid, one out of five drum cans was melted using 100 V, 750
W band heaters, and the melted acid was taken out using a plastic hand pump. The work was
repeated many times. The can exploded on the third day after the heater was turned off and the
can was capped. The lid of the drum can blew off and there was a vapor explosion of about 100
L of acrylic acid because of a rapid pressure drop. The mist dispersed in the air ignited and
exploded [26].
The following cycle was repeated: Partial melting, taking out of liquid, solidification. The
polymerization inhibitor for preventing a runaway reaction was transferred from solidified acid
to liquid acid. As a result, the concentration of the inhibitor in the solidified acrylic acid seems
to have become lower. With contamination by iron rust during the work or in the austenitic
stainless steel material of the drum can, a polymerization reaction was promoted, and a runaway
reaction progressed [35].
32
C h a p t e r F o u r : H a za r d s a n d O p e r a b i l i t y S t u d y ( H A Z O P )
CHAPTER FOUR
Hazards and Operability Study (HAZOP)
4.1
Introduction
Hazard and Operability Study (HAZOP) is a structured and systematic technique for system
examination and risk management. The HAZOP technique was initially developed to analyze
chemical process systems, but has later been extended to other types of systems and also to
complex operations and to software systems [36]. HAZOP is also commonly used in risk
assessments for industrial and environmental health and safety applications.
The purpose of a HAZOP study is to identify potential hazards under all foreseeable conditions.
A HAZOP study can also be used in part as a training aid for plant personnel and in the
preparation of Operating Manuals. The HAZOP study can be used on a new or existing
procedures, organisation changes, or operational activity. Besides, it also acts as a way of
rigorously and systematically checking a design for safety, operability and conformity with
codes of practice etc.
HAZOP is based on a theory that assumes risk events are caused by deviations from design or
operating intentions. Identification of such deviations is facilitated by using sets of guide
words as a systematic list of deviation perspectives. This approach is a unique feature of the
HAZOP methodology that helps stimulate the imagination of team members when exploring
potential deviations.
The success or failure of a HAZOP study depends on several factors, such as the completeness
and accuracy of drawings, the technical skills and insights of the team, the ability of the team
to use the approach as an aid to their imagination in visualizing deviations, and the ability of
the team to concentrate on the more serious hazards.
33
Prior to a HAZOP assessment, a few materials are usually needed. These include process
description, process flowsheets, piping and instrumentation diagrams, operating procedures,
maintenance procedures, emergency response procedures, and the chemical, physical, and
toxicological properties of all raw, intermediate and product materials that are involved in the
process.
An important step of a HAZOP analysis is to form a competent team comprised of different
disciplines and experiences. The method is based on the principle that people with distinct
experiences and training can interact better and identify more problems together generating
ideas. In this study, a team leader will act as a coordinator that ensures that the correct
procedure is followed and that no significant aspects are left out, stimulating discussion, etc.
It is helpful to define the terms that are usually used in a HAZOP analysis study:
Study nodes: the locations (on piping and instrumentation drawings and procedures) at which
the process parameters are investigated for deviations.
Intention: the intention defines how the plant is expected to operate in the absence of
deviations at the study nodes. This can take a number of forms and can either be descriptive or
diagrammatic; e.g., flowsheets, and line diagrams.
Deviations: departures from the intention which are discovered by systematically applying the
guide words (e.g., "more pressure").
Causes: the reasons why deviations might occur. Once a deviation has been shown to have a
credible cause, it can be treated as a meaningful deviation. These causes can be hardware
failures, human errors, an unanticipated process state (e.g., change of composition), external
disruptions (e.g., loss of power), etc.
Consequences: the results of the deviations should they occur (e.g., release of toxic materials).
Guide Words: simple words which are used to qualify or quantify the intention in order to
guide and stimulate the brainstorming process and so discover deviations.
34
4.2
Guide Words and Parameters
The guide words are used to ensure that the design is explored in every conceivable way. Thus,
the team must identify a fairly large number of deviations, each of which must then be
considered so that their potential causes and consequences can be identified. A HAZOP uses
parameters and guidewords to suggest deviations or process variables and their causes [37]. A
standard set of guide words is given in Table 4.1. Typical parameters are flow rate, pressure,
temperature, level, composition, flow quantity and physical properties such as viscosity.
Table 4.6 Typical guide words used in HAZOP analysis [36]
Guide Words
Meaning
Comments
NO, NOT, NONE
The complete negation of

these intentions
No part of the intentions is

achieved
MORE OF and
LESS OF
Quantitative increases or
decreases
Refer to quantities and

properties such as flow rates
PART OF
A qualitative decrease
Only some of the intentions

are achieved
REVERSE
The logical opposite of the

intention
Applicable to activities such as

chemical reactions
OTHER (THAN)
Complete substitution
No part of the original

intention is achieved
AS WELL AS
A qualitative increase
All intentions are achieved

with some additional activity
4.3
Study Nodes
Four major equipment (reactor, absorber, heat exchanger, and tower) and four nodes are
selected for HAZOP analysis. These equipment were hand-picked mainly due to concerns of
the high temperatures involved.
Node 1: The stream starts from the feed mixture to reactor (R-301)
Node 2: The stream starts from the quench tower (T-301) to absorber (T-302).
Node 3: The stream starts from pump (P-302) to heat exchanger (E-302).
Node 4: The stream starts from the extract unit (X-301) to acid tower (T-303).
35
Chapter Four: Hazards and Operability Study (H AZOP )
Equipment
Reactor (R-301)
Node 1
Inlet to reactor (R-301)
Node No. 1
Starts from the feed (propylene, steam and air) mixture to reactor (R-301)
Intention
To transport the mixture of (propylene, steam and air) from the feed to R-301
Parameter
Flow
Table 4.7 HAZOP analysis for node 1 Flow

No.
Guide word
Deviation
Causes
Consequences
Actions
Regular operator
patrol of all lines
Install control
Valve(s) closed or
1
NO
No flow of the mixture
jammed Power
failure
Flow stopped
Line breakage
36
Process stops
No product
valves that fails

open
Install flow
indicator and flow
control valve
Install low flow
alarm
Install shut down
valve
No.
Guide word
MORE
Deviation
More flow of the

mixture
Causes
Standby pump is
running together
with the service
pump
Increased pumping
capacity
Flow control valve
Consequences
Actions
More propylene,
steam and air in R301
Pipe rupture
Ensure continuity of
(propylene, steam
and air) and good
communications
from feed storage
Install high level
alarm
Install flow
indicator and flow
control valve
Product not
according to the
desire
specifications
Reduced production
Install low level

alarm
Regular operator
patrol of all lines
Failure
LESS
Less flow of the

mixture
Pipe leakage or
blockage
C-301 A/B failure
Sediment in the
pipe
Valve not fully
open
Leaking flange
37
No.
Guide word
REVERSE
AS WELL AS
Deviation
Causes
Consequences
Reverse flow of the

mixture
Incorrect pressure
differential
C-301 A/B failure
Non-return valve
failure
C-301 A/B reverse
Back flow to the

feed tanks
Product not
according to desired
specifications
Install check valve

Install non-return
valve
Formation of byproducts in the

production
Poor quality of
product
Process stops
Test quality of feed

regularly
Impurities
Poor quality feed
38
Actions
Equipment
Reactor (R-301)
Node 1
Node No. 1
Intention
Parameter
Temperature
Table 4.8 HAZOP analysis for node 1 Temperature

No.
Guide word
Deviation
Causes
Ambient condition
Defective control
1
MORE
High temperature
valve
Temperature
controller
malfunctioning
Preheater operating
above rated
capacity
39
Consequences
Higher temperature
in the R-301
(expulsion)
High temperature
may cause
flammable pipe
(may cause fire)
Product not
according to the
desire
specifications
Actions
Install temperature
indicator
Install high
temperature alarm
Installed trip alarm

for very high
temperature
No.
Guide word
LESS
Deviation
Low temperature
Causes
Ambient condition
Temperature
controller
malfunctioning
Equipment
Reactor (R-301)
Node 1
Node No. 1
Intention
Parameter
Pressure
40
Consequences
Low temperature in
the reactor
Product not
according to the
desire
specifications
Actions
Install temperature
indicator
Install low
temperature alarm
Table 4.9 HAZOP analysis for node 1 Pressure

No.
Guide word
Deviation
Causes
Relief valve
MORE
High pressure
isolated
Pressure controller
malfunctioning
Less/no flow of the
mixture
Partial blockage of
line due to partially
closed valve
Consequences
Actions
Potential damage to
the R-301 if
isolated from the
relief valve
Product not
according to the
desire
specifications
R-301 may explode
Install pressure
relief valve with
automatic feed from
temperature control
system
Install high pressure
alarm
Potential
LESS
Low pressure
Restricted pump
Pipe leakage
41
malfunction of R301
Product not
according to the
desire
specifications
Install low pressure

alarm
Equipment
Reactor (R-301)
Node 1
Node No. 1
Intention
Parameter
Composition
Table 4.10 HAZOP analysis for node 1 Composition

No.
Guide word
Deviation
CHANGE
Composition change
Causes
Process control
upset
Leaking isolation
valves
42
Consequences
Product not
according to the
desire
specifications
Actions

regularly
Equipment
Off-Gas Absorber (T-302)
Node 2
Inlet to Off-Gas Absorber (T-302)
Node No. 2
Starts from the Quench Tower (T-301) to Absorber (T-302)
Intention
To transport the mixture from the Quench Tower (T-301) to the Absorber (T-302)
Parameter
Level
Table 4.11 HAZOP analysis for node 1 Level

No.
Guide word
Deviation
Causes
Consequences
Inflow greater than

1
High
High level
outflow
Pressure surge
Corrosion
43
Limited mass
transfer
Product not
according to the
desire
specifications
Actions
Install level sensor

on absorber
No.
Guide word
Low
Deviation
Low level
Causes
Leak
Outflow greater
than inflow
Inlet flow stop
Control failure
Equipment
Node 2
Node No. 2
Intention
Parameter
Temperature
44
Consequences
Limited mass
transfer
Product not
according to the
desire
specifications
Actions
Install level sensor

on absorber

No.
Guide word
Deviation
Causes
Ambient condition
Defective control
1
MORE
LESS
High temperature
Low temperature
valve
Temperature
controller
malfunctioning
Too much cooling

power
Reducing pressure
Temperature
controller
malfunctioning
45
Consequences
Higher temperature
in the T-302
(expulsion)
Some of the
components start to
vaporize
Product not
according to the
desire
specifications
Actions
Install temperature
sensor
Install high
temperature alarm
Install temperature
indicator
Install low
temperature alarm
Equipment
Node 2
Node No. 2
Intention
Parameter
Pressure

No.
Guide word
Deviation
Causes
Leak
Pressure controller
1
MORE
High pressure
malfunctioning
Less/no flow of the

mixture
46
Consequences
Product not
according to the
desire
specifications
T-302 may explode
Actions
Install pressure
relief valve with
automatic feed from
temperature control
system
alarm
No.
Guide word
Deviation
Causes
Consequences
Actions
Pressure in the
2
LESS
Low pressure
Absorber is over
cooled
leakage
Equipment
Node 2
Node No. 2
Intention
Parameter
Composition
47
system drops
Product not
according to the
desire
specifications

alarm

No.
Guide word
Deviation
Causes
Process control
1
CHANGE
Composition change
Equipment
Quench Cooler (E-302)
Node 3
Inlet to Heat exchanger (Cooler) (E-302)
Node No. 3
Starts from pump (P-302) to heat exchanger (E-302)
Intention
Transport the fluid from (P-302) to Quench Cooler (E-302)
Parameter
Flow
upset
Incorrect feedstock
specification
48
Consequences
Product not
according to the
desire
specifications
Actions

regularly

No.
Guide word
Deviation
Causes
NO
No flow
MORE
More flow
Failure of
previous
equipment
Control valve
failure
Valve closed or
jammed
Power failure
Flow stopped
Line breakage
Control valve trim

changed
Cross connection of
systems
49
Consequences
Actions
Process interruption
No product
Regular operator
patrol of all lines
Install control
valves that fails
open
Install flow
indicator and flow
control valve
Install low flow
alarm
Install shut down
valve
Flooding
Increase pressure
Shutdown the
process
Install flow
controller
No.
Guide word
Deviation
LESS
Less flow
REVERSE
Reverse flow
Causes
Valve failure
Pipe blockage
Non-return valve
failure
Backflow due to
back pressure from
downstream
50
Consequences
Actions
Less distillate rate

Product not
according to desire
specification
Fit flow alarm

Check on valve and
pipe
Back flow to the

pump
Product not
according
specification
Install check valve

Install non-return
valve
No.
Guide word
AS WELL AS
Deviation
Impurities
Equipment
Node 3
Node No. 3
Intention
Parameter
Temperature
Causes
Poor quality feed
51
Consequences

production
Low purity
products
Process stops
Actions

regularly

No.
Guide word
Deviation
Causes
MORE
High temperature
LESS
Low temperature
52
Consequences
Actions
Hot weather
Fire near the heat
exchanger
Low cooling
water
High temperature
of cooling water
Ambient condition
Thermal expansion
in an isolated valve
Temperature
controller
malfunctioning
Cold weather
High cooling
water
Low temperature
of cooling water
Ambient condition
Temperature
controller
malfunctioning
Install
temperature
indicator
Install high
temperature alarm
Installed trip
alarm for very
high temperature
Install
temperature
indicator
Install low
temperature alarm
Equipment
Node 3
Node No. 3
Intention
Parameter
Pressure

No.
Guide word
Deviation
Causes
Pressure controller
MORE
High pressure
malfunctioning
Relief valve
isolated
Less/no flow of the
mixture Relief
valve fails closed
Pipeline blockage
53
Consequences
Actions
Excess pressure
Install pressure
(may cause
explosion)
Product not
according to the
desire
specifications
relief valve with

automatic feed from
temperature control
system
alarm
No.
Guide word
LESS
Deviation
Causes
Low pressure
Pipe/flange leakage
Pressure controller
malfunctioning
Generation of
vacuum condition
Equipment
Node 3
Node No. 3
Intention
Parameter
Composition
54
Consequences
Actions
Temperature may
increase in the heat
exchanger
Product not
according to the
desire
specifications

alarm

No.
Guide word
Deviation
Causes
Process control
1
CHANGE
Composition change
Equipment
Acid Tower (T-303)
Node 4
Inlet to T-303
Node No. 4
Starts from the extract unit (X-301) to (T-303)
Intention
Transport the fluid from (X-301) to (T-303)
Parameter
Flow
upset
Leaking exchanger
tubes
55
Consequences
Product not
according to the
desire
specifications
Actions

regularly

No.
Guide word
NO
MORE
Deviation
No flow
More flow
Causes
Consequences
Valve closed or
jammed
Failure of previous
equipment
Flow stopped
Line breakage
Power failure
Process interruption
No product
distillation column
fails (process stops)
Control valve trim

changed
Cross connection of
systems
Flooding
Increase pressure
Pressure increases
in the pipe (may
cause pipe rupture)
56
Actions
Regular operator
patrol of all lines
Install control
valves that fails
open
Install flow
indicator and flow
control valve
Install low flow
alarm
Install shut down
valve
Shutdown the
process
Install flow
controller
No.
Guide word
LESS
REVERSE
Deviation
Less flow
Reverse flow
Causes
Valve failure
Pipe blockage
Non-return valve
failure
Backflow due to
back pressure from
downstream
57
Consequences
Actions
Less distillate rate

Product not
according to desire
specification
Check on valve and

pipe
Install flow
indicator and flow
control valve
Back flow to the

vaporizer
Product not
according
specification
liquids release to
the work area
Install check valve

Install non-return
valve
No.
Guide word
AS WELL AS
Deviation
Impurities
Equipment
Acid Tower (T-303)
Node 4
Inlet to acid Tower (T-303)
Node No. 4
Intention
Parameter
Temperature
Causes
Poor quality feed
58
Consequences

production
Low purity
products
Process stops
Actions

regularly

No.
Guide word
MORE
LESS
Deviation
Causes
High temperature
Fuel controller
malfunctioning
Ambient condition
Fire near the
distillation column
Low temperature
Cold weather
Temperature
controller
malfunctioning
Distillation column
Boiler failure
59
Consequences
Actions
Product not
according to the
desire
specifications
Install temperature
indicator
Install low
temperature alarm
Check the fuel flow
and temperature
controller
Product not
according to the
desire
specifications
Install temperature
indicator
Install high
temperature alarm
Installed trip alarm
for very high
temperature
Equipment
Acid Tower (T-303)
Node 4
Inlet to T-301
Node No. 4
Intention
Parameter
Pressure

No.
Guide word
MORE
Deviation
High pressure
Causes
Consequences
Pressure controller
Increase pressure
malfunctioning
Relief valve
isolated
Partial blockage of
line due to partially
closed valve
Pipeline blockage
Excess pressure
60
upstream
(may cause
explosion)
Product not
according to the
desire
specifications
Actions
Install pressure
relief valve with
automatic feed from
temperature control
system
alarm
No.
Guide word
LESS
Deviation
Low pressure
Causes
Pipe/flange leakage
Pressure controller
malfunctioning
Generation of
vacuum condition
61
Consequences
Temperature may
increase in T-303
Product not
according to the
desire
specifications
Low pressure
leading to reverse
flow
Release the
materials to the
work area
Actions

alarm
Install control
pressure valve
Ch a p te r Fi ve : E q u ip me n t De s ign
CHAPTER FIVE
Equipment Design
Part One: Heat Exchangers

5.1
Background of Heat Exchangers
5.2
Sizing of Cooler E-302
5.3
Sizing of Reboiler E-303
5.4
Design of Condenser E-304
5.5
Design of Cooler E-305
Part three
62
Part One
Heat Exchangers
63
5.1
Background of Heat Exchangers
5.1.1 Definition
A heat exchanger is a piece of equipment built for efficient heat transfer from one medium to
another. The media may be separated by a solid wall to prevent mixing or they may be in direct
contact [38]. They are widely used in space heating, refrigeration, air conditioning, power
plants, chemical plants, petrochemical plants, petroleum refineries, natural gas processing, and
sewage treatment.
The classic example of a heat exchanger is found in an internal combustion engine in which a
circulating fluid known as engine coolant flows through radiator coils and air flows past the
coils, which cools the coolant and heats the incoming air.
5.1.2 Flow Arrangement

There are four primary classifications of heat exchangers according to their flow arrangement.
In parallel-flow heat exchangers, the two fluids enter the exchanger at the same end, and travel
in parallel to one another to the other side. In counter-flow heat exchangers the fluids enter the
exchanger from opposite ends. The counter current design is the most efficient, in that it can
transfer the most heat from the heat (transfer) medium due to the fact that the average
temperature difference along any unit length is greater. The third classification is cross-flow
heat exchangers, where the fluids travel roughly perpendicular to one another through the
exchanger. Finally, the so-called regenerative heat exchangers are used in some industries,
where heat is stored to be released later.
5.1.3 Types of Heat Exchangers

5.1.3.1 Shell and Tube Heat Exchanger
Shell and tube heat exchangers, shown in Figure 5.1, consist of a series of tubes. One set of
these tubes contains the fluid that must be either heated or cooled. The second fluid runs over
the tubes that are being heated or cooled so that it can either provide the heat or absorb the heat
required. A set of tubes is called the tube bundle and can be made up of several types of tubes:
plain, longitudinally finned, etc [39].
64
Figure 5.1 Shell and tube heat exchanger
5.1.3.2 Plate Heat Exchanger

A plate heat exchanger, as the one shown in Figure 5.2, is composed of multiple, thin, slightly
separated plates that have very large surface areas and fluid flow passages for heat transfer.
This stacked-plate arrangement can be more effective, in a given space, than the shell and tube
heat exchanger.
Figure 5.2 An interchangeable plate heat exchanger
5.1.3.3 Plate and Shell Heat Exchanger

Combines plate heat exchanger with shell and tube heat exchanger technologies. The heart of
the heat exchanger contains a fully welded circular plate pack made by pressing and cutting
round plates and welding them together.
65
5.1.3.4 Double Pipe Heat Exchanger

Double pipe heat exchangers are the simplest exchangers used in industries. On one hand, these
heat exchangers are cheap for both design and maintenance, making them a good choice for
small industries. But on the other hand, low efficiency of them besides high space occupied for
such exchangers in large scales, has led modern industries to use more efficient heat exchanger
like shell and tube or other ones.
5.1.3.5 Fluid Heat Exchanger
This is a heat exchanger with a gas passing upwards through a shower of fluid (often water),
and the fluid is then taken elsewhere before being cooled. This is commonly used for cooling
gases whilst also removing certain impurities, thus solving two problems at once. It is widely
used in espresso machines as an energy-saving method of cooling super-heated water to use in
the extraction of espresso [40].
5.1.3.6 Waste Recovery Heat Exchanger
A Waste Heat Recovery Unit (WHRU) is a heat exchanger that recovers heat from a hot gas
stream while transferring it to a working medium, typically water or oils. The hot gas stream
can be the exhaust gas from a gas turbine or a diesel engine or a waste gas from industry or
refinery.
5.1.4 Classification According to Process Function

Heat exchangers are classified according to process function into condensers, heaters, coolers
and liquid to vapor phase change exchangers (reboilers and vaporizers).
5.1.4.1 Condensers
A condenser, as the one shown in Figure 5.3, is a device or unit used to condense a substance
from its gaseous to its liquid state, typically by cooling it. In so doing, the latent heat is given
up by the substance, and will transfer to the condenser coolant. Condensers are typically heat
exchangers which have various designs and come in many sizes ranging from rather small
(hand-held) to very large industrial-scale units used in plant processes [41].
66
Figure 5.3 Diagram of a typical water-cooled surface condenser
Condensers are used in air conditioning, industrial chemical processes such as distillation,
steam power plants and other heat-exchange systems. Use of cooling water or surrounding air
as the coolant is common in many condensers.
The construction of a condenser will be similar to other shell and tube exchangers, but with a
wider baffle spacing. Four condenser configurations are possible (see Table 5.1). Horizontal
shell-side and vertical tube-side are the most commonly used types of condenser. A horizontal
exchanger with condensation in the tubes is rarely used as a process condenser, but is the usual
arrangement for heaters and vaporizers using condensing steam as the heating medium [42].
Table 5.1 Possible condenser configurations
Arrangement
Condensation
Cooling Medium
Horizontal
Shell
Tube
Horizontal
Tube
Shell
Vertical
Shell
Tube
Vertical
Tube
Shell
The normal mechanism for heat transfer in commercial condensers is film-wise condensation.
Drop-wise condensation will give higher heat-transfer coefficients, but is unpredictable; and is
not yet considered a practical proposition.
67
5.1.4.2 Liquid to Vapor Phase Change Exchangers (Reboilers and Vaporizers)

Liquid to vapor phase change exchangers are devices which heat and vaporize a working fluid.
In many cases, they are similar to industrial boilers except that they do not build up high
pressures. Vaporizer and reboiler units are most commonly used for low pressure heat transfer
by incorporating the vaporized stream as the heat exchange fluid. They can also be used to
vaporize liquid fuels or cryogenic liquids.
Generally, there are three types of liquid to vapor phase changers:
Forced circulation
In this type, the fluid is pumped through the exchanger, and the vapor formed is separated in
the base of the column (see Figure 5.4). When used as a vaporizer a disengagement vessel will
have to be provided.
Figure 5.4 Forced-circulation reboiler
Thermosyphon (natural circulation)
It has vertical exchangers with vaporization in the tubes, or horizontal exchangers with
vaporization in the shell (see Figure 5.5). The liquid circulation through the exchanger is
maintained by the difference in density between the two-phase mixture of vapor and liquid in
the exchanger and the single-phase liquid in the base of the column. As with the forcedcirculation type, a disengagement vessel will be needed if this type is used as a vaporizer.
68
Figure 5.5 Horizontal thermosyphon reboiler
Kettle reboiler
In this type, boiling takes place on tubes immersed in a pool of liquid; there is no circulation
of liquid through the exchanger (see Figure 5.6). This type is also, more correctly, called a
submerged bundle reboiler.
Figure 5.6 Kettle reboiler
In case a vaporizer is desired, the selection of the type depends on the following factors
The nature of the process fluid, particularly its viscosity and propensity to fouling.
The operating pressure: vacuum or near critical pressure.
The equipment layout, particularly the headroom available.
69
5.1.5 Heat Exchanger Design Equations

5.1.5.1 Preliminary
The heat load is calculated by the following equation
Q = n Cp (T2 -T1 )
(5.1)
Where n is the molar flowrate in kmol/h and Cp is the heat capacity. The mean temperature
difference, or the mean driving force for a counter-current process is defined by
Tlm =
(T1 - t2 ) - (T2 - t1 )
T -t
ln (T1 - t2 )
2
1
(5.2)
The capital letter temperature designates the hot fluid and the small letter temperature
designates the cold fluid. However, due to the two tube passes used here, this temperature must
be corrected using a correction factor, such that
Tm = Ft Tlm
(5.3)
The correction factor Ft is a function of the shell and tube temperatures, and the number of
tubes and shell passes. It is normally correlated as a function of two dimensionless temperature
ratios
R=
T1 - T2
t2 - t1
(5.4)
S=
t2 - t1
T1 - t1
(5.5)
And,
The values of R and S are then substituted into equation (5.6) to solve for Ft
Ft =
R2 +1 ln ( 1 - S )
1 - RS
2 - S (R + 1 - R2 + 1)
(R - 1) ln (
)
2 - S (R + 1 + R2 + 1)
70
(5.6)
The required surface area is then calculated as follows
A=
Q
U Tm
(5.7)
Where Q is the heat load as defined by equation (5.1), U the overall heat transfer coefficient,
and Tm the corrected temperature as defined by equation (5.3). The number of tubes can be
calculated by dividing the total area, given in equation (5.7), by the area of one tube. In other
words
Nt =
A
do L
(5.8)
The bundle diameter can be calculated as follows

1
Nt n 1
Db = do ( )
K1
(5.9)
Where K1 and n1 are constants depending on the arrangement of tubes (triangular or square)
and the number of tube passes. Table 5.2 gives values for different arrangements and different
number of passes.
Table 5.2 Bundle diameter constants for triangular and square pitches [42]
Triangular Pitch (Pt = 1.25 do)
No. Passes
K1
0.319
0.249
0.175
0.0743
0.0365
n1
2.142
2.207
2.285
2.499
2.675
Square Pitch (Pt = 1.25 do)

No. Passes
K1
0.215
0.156
0.158
0.0402
0.0331
n1
2.207
2.291
2.263
2.617
2.643
71
The shell diameter must be selected to give as close a fit to the tube bundle as is practical; to
reduce bypassing round the outside of the bundle. The clearance required between the
outermost tubes in the bundle and the shell inside diameter will depend on the type of exchanger
and the manufacturing tolerances; typical values are given in Figure 5.7.
Figure 5.7 Shell-bundle clearance [42]
Since designing a heat exchanger follows a trial and error procedure, a close first assumption
of the overall heat transfer coefficient is needed for convergence. Therefore, typical values are
listed in Table 5.3.
Table 5.3 Typical overall coefficients [42]
Hot Fluid
Cold Fluid
U (W/m2 C)
Organic Solvents
Water
250 750
Light Oils
Water
350 900
Heavy Oils
Water
60 300
Gases
Water
20 300
Organic Solvents
Brine
150 500
Water
Brine
600 1200
72
5.1.5.2 Tube-Side
This section is devoted to estimating the inside convective heat transfer coefficient. One of the
best correlations for water (tube-side fluid) is given by Eagle and Ferguson [42]
hi =
4200(1.35 + 0.02t)u0.8
t
d0.2
i
(5.10)
Where t is the inside average temperature in C, ut the water velocity in m/s, and di the tube
inside diameter in mm.
5.1.5.3 Shell-Side
The outside convective heat transfer coefficient for acrylic acid will be calculated using Kerns
method. The first step is to calculate the area for cross-flow As for hypothetical row of tubes
As =
(pt - do )Ds lB
(5.11)
pt
Where pt is the tube pitch, Ds the shell diameter, and lB the baffle spacing. Next, the equivalent
diameter for a square pitch arrangement is calculated
de =
1.27 2
(pt - 0.785d2o )
do
(5.12)
de =
1.1 2
(p - 0.917d2o )
do t
(5.12)
For triangular pitch
The shell-side Reynolds number is calculated by
Re =
us de
(5.13)
Where us is the shell-side velocity and de is the effective diameter as given by equation (5.12).
The density and viscosity are calculated at the mean temperature of the inlet and outlet streams.
The value of the Reynolds number is substituted into Figure 5.8 to solve for jh factor.
73
The outside convective heat transfer coefficient is finally calculated by the following
ho =
1
kf
jh Re P3r ( )
de
w
0.14
(5.14)
Most of the times the viscosity term is close to unity and can be neglected
5.1.5.4 Overall Coefficient
In order to check whether the assumed overall coefficient is correct or not, the following
equation is employed
-1
d
do ln ( o ) d
1
1
1
d
1
di
o
o
Uo = [ +
+
+
+
]
ho hod
2kw
di hid di hi
(5.15)
Where Uo is the overall coefficient based on the outside area of the tube, ho the outside fluid
film coefficient, hi the inside fluid film coefficient, hid the inside fouling factor, hod the outside
fouling factor, and kw the thermal conductivity of the tube wall material.
8.4.5.5 Pressure Drop
The pressure drop for the tube-side is given by the following
-m
u2t
Pt = Np (8 jf ( ) ( ) + 2.5)
di
w
2
(5.16)
Where Np is the number of tube-side passes and jf the tube friction factor given by Figure 5.9.
The Reynolds number is the same as that given in equation (5.13) but with a slight
modification; the tube velocity ut is used instead of the shell velocity us and the inside diameter
di instead of the effective diameter de .
The shell-side pressure drop is calculated in a similar manner
-0.14
Ps = 8 jf (
Ds
L
u2s
)( )
( )
de
lB
2
w
74
(5.17)
Where jf is the shell friction factor given by Figure 5.10 and lB the baffle spacing. The viscosity
term is usually close to unity and hence can be neglected.
Figure 5.8 Shell-Side heat transfer factor [42]
Figure 5.9 Tube-Side friction factor [42]
75
Figure 5.10 Shell-Side friction factor [42]
5.1.6 Horizontal Condenser Design Equations

5.1.6.1 Preliminary
The same equations discussed in section 5.1.5.1 are used here as well.
5.1.6.2 Tube-Side
The same equations discussed in section 5.1.5.2 are used here as well.
5.1.6.3 Shell-Side
The physical properties of the condensate for use in the following equations, are evaluated at
the average condensate film temperature: the mean of the condensing temperature and the tubewall temperature. The wall temperature is calculated as follows
Tw = TAVG
U
(TAVG tAVG )
hc
(5.18)
The condensing coefficient hc is initially assumed. To check the accuracy of the assumption,
Kerns method is used [42]
76
1
1
( v )g 3
hc = 0.95kL [ L L
] Nr6
L h
(5.19)
Where L and v are the liquid and vapor condensate densities, respectively, L the condensate
viscosity, and Nr the average number of tubes in a vertical row. The quantity h is defined as
follows
h =
Wc
LNt
(5.20)
Where Wc is the total mass condensate flow, L the tube length, and Nt the total number of tubes
in the bundle. Nr can be taken as two-thirds of the number in the central tube row.
5.1.6.4 Overall Coefficient
In order to check whether the assumed overall coefficient is correct or not, the following
equation is employed
1
do
d
ln
(
)
o
1
1
do 1
do 1
di
Uo = [ +
+
+
+
]
hc hcd
2kw
di hid di hi
(5.21)
Where Uo is the overall coefficient based on the outside area of the tube, hc the condensing
coefficient, hi the inside fluid film coefficient, hid the inside fouling factor, hcd the outside
fouling factor, and kw the thermal conductivity of the tube wall material.
5.1.6.5 Pressure Drop
The same equations discussed in section 5.1.5.4 are used here but with one exception. The
shell-side pressure drop is 50% of that calculated using the inlet flow
0.14
Ps =
1
Ds
L
u2s
[8 jf ( ) ( )
( )
2
de
lB
2
w
77
(5.22)
5.1.7 Thermosyphon Reboiler Design Equations

The heat load is defined by the same equation given in previous sections. Since the inlet and
outlet streams are at the same temperature, the mean overall temperature difference is used
Tm = T - t
(5.23)
The uppercase letter temperature designates the saturated steam temperature and the lowercase
letter temperature designates the boiling temperature. The reduced temperature is then
calculated by the following equation
Tr =
T
TC
The design heat flux q is obtained by reading both Tr and Tm from Figure 5.11
Figure 5.11 Vertical thermosyphon correlation [42]
78
(5.24)
The required surface area is then calculated as follows

A=
Q
q
(5.25)
Where Q is the heat load and q is the design heat flux obtained from Figure 5.11. The number
of tubes can be calculated by dividing the total area, given by equation (5.25), by the area of
one tube. In other words
Nt =
A
di L
(5.26)
The bundle diameter, shell diameter, and clearance are calculated in the same manner described
in section 5.1.5.1. The outer pipe diameter is calculated as follows
AC
do =
4
(5.27)
Where AC is the tube cross-section area defined by the following

AC =
dL
4 i
(5.28)
5.1.8 Design Assumptions

Unless otherwise stated, the following assumptions are made for all subsequent heat exchanger
designs (heat exchangers, condensers, reboilers, etc.).
Steady state process.
The heat lost by the hot fluid is completely gained by the cold fluid.
The overall heat transfer coefficient U is constant.
Equal heat transfer area in each pass.
The temperature of the shell side is constant radially.
No direct contact between the hot and cold fluid.
Thermal conductivity is considered constant through the tube.
Any missing data that are not considered here will be mentioned in design calculations.
79
5.2
Sizing of Cooler E-302
5.2.1 Problem Statement

In the production of acrylic acid, the product (acrylic acid) and by-product (acetic acid) along
with deionized water are mixed and pumped using P-302 A/B with the majority of liquid water
at a temperature of 50 C and a pressure of 2.4 bar. Size a heat exchanger E-302 to cool down
this mixture to the desired temperature of 40 C. Water will be used as the coolant, with a
temperature rise from 25 C to 40 C.
5.2.2 Design Considerations

The specifications of the internal components, such as: the inside and outside diameters of the
tubes, number of shell and tube passes, pitch type, etc., are necessary in design calculations.
These are listed in Table 5.4.
Table 5.4 Internal component specifications of E-302
Internal Component
Specification
Shell Passes
Tube Passes
Tube Thickness
1.7
Tube Outer Diameter do (mm)
19
Tube Internal Diameter di (mm)
15.6
Tube Length (m)
7.22
Tube Material of Constructions
Stainless Steel 318
Pitch Type
Triangle
Pitch Spacing (mm)
23.75
Baffle Type
Single segmental baffle
Baffle Spacing
Two fifths the shell diameter
Baffle Cut percentage
25%
80
5.2.3 Inlet and Outlet Streams

X (Water) = 0.9257
X (Acetic Acid) = 0.0049
X (Acrylic Acid) = 0.0694
X (Water) = 0.9257
Hot Stream (T = 40 C)
Cold Stream (t = 40 C)
E-302
Figure 5.15 Arrangement of inlet and outlet streams
Figure 5.12 is a visual representation of the inlet and outlet streams for heat exchanger E-302.
Table 5.5 summarizes the flowrates along with the corresponding temperatures and pressures.
Table 5.5 Inlet and outlet stream conditions and flowrates
Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Water
Acetic Acid
Acrylic Acid
10
50
2.4
144048.06
757.98
10803.24
10
40
2.4
144048.06
757.98
10803.24
Coolant In
25
1.0
0.00
0.00
Coolant Out
40
1.0
0.00
0.00
The superscript dash indicates the outlet stream of the heat exchanger. Unfortunately, the
flowrate is extremely high which will result in a very large heat exchanger. To solve this
problem, the mixture is divided into four streams of equal flowrates each of which is fed to a
separate similar heat exchanger. The modified flowrates are summarized in Table 5.6.
Table 5.6 Inlet and outlet stream conditions and flowrates for one heat exchanger
Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Water
Acetic Acid
Acrylic Acid
Mixture In
50
2.4
36012.02
189.50
2700.81
Mixture Out
40
2.4
36012.02
189.50
2700.81
Coolant In
25
1.0
0.00
0.00
Coolant Out
40
1.0
0.00
0.00
81

In order to carry out design calculations, the physical properties of water, acrylic acid and acetic
acid are needed. These properties include the density, viscosity, thermal conductivity, etc. For
a sizing problem, however, the only property that is needed is the heat capacity. Since this
property varies with temperature, it will be calculated at the average temperature between the
inlet and outlet streams. Therefore,
TAVG =
T1 + T2 50 + 40
=
= 45 C
2
2
tAVG =
t1 + t2 25 + 40
=
= 32.5 C
2
2
And,
The specific heat capacity at the average temperature for each component is given in Table 5.7.
Table 22.7 Specific heat capacity of each component at the average temperatures [43]
Component
Specific Heat Capacity (kJ/kmol-K)

Hot Fluid (TAVG = 45 C)
Water
75.825
Acetic Acid
128.480
Acrylic Acid
150.660
Cold Fluid (tAVG = 32.5 C)
Water
75.300
The average specific heat capacity of the hot fluid mixture is calculated as follows
Acrylic
CMix
= (XWater ) (CWater
) + (XAcetic ) (CAcetic
) + (XAcrylic ) (CP
P
P
P
Plugging in the numbers,

CMix
= (0.9257) (75.825) + (0.0049) (128.480) + (0.0694) (150.660) = 81.3
P
82
kJ
kmolK
5.2.5 Calculations
5.2.5.1 Preliminary Calculations
Applying Equation (5.1) to calculate the heat load
Q = 38902.32 81.3 (50 40) = 31618619.583 kJ/h
Since no heat losses to the surrounding is assumed, e.g. heat lost by the hot fluid is gained by
the cold fluid, we can calculate the flowrate of water by rearranging equation (5.1)
nW =
31618619.583
= 27994.47 kmol/h
75.3 (40.00 25.00)
Next we calculate the mean temperature using Equation 5.2
Tlm =
(50 40) (40 25)

= 12.33 C
50 40
ln (
)
40 25
Since we are using a 1 shell/2 tube pass heat exchanger, a temperature correction is necessary.
Using Equations 5.4 and 5.5
R=
50 40
= 0.667
40 25
S=
40 25
= 0.600
50 25
And,
Substituting the values of R and S into equation (5.6)
Ft =
1 0.600
0.6672 + 1 ln (
1 0.667 0.600)
2 0.600 (0.667 + 1 0.6672 + 1)
(0.667 1) ln (
)
2 0.600 (0.667 + 1 + 0.6672 + 1)
83
= 0.801
The mean temperature is then corrected using equation (5.3)

Tm = 0.801 12.33 = 9.878 C
5.2.5.2 Fluid Allocation and Fouling Factors
In allocating fluids to either sides, different factors must be taken into consideration. These
factors include the corrosive nature or fouling factors of the fluids, operating pressures and
temperatures, etc. In almost all cases, the fluid with the highest fouling factor will be assigned
to the tube-side, as it allows for ease of cleaning. Water has the highest fouling factor and is
present in both the hot and cold fluids. However, since it is present in the hot fluid in greater
proportions, the hot fluid will be assigned to tube-side.
5.2.5.3 Overall Heat Transfer Coefficient Calculations
The next step is to assume an overall heat transfer coefficient. Since the hot fluid consists
mainly of water, the following value will be assumed (see Table 5.3)
U = 1000
W
m2 C
Calculating the corresponding surface area using equation (5.7) and taking into account units
homogeneity
A=
31618619.583 1000
= 889.183 m2
3600 1000 9.878
Using equation (5.8) to calculate the number of tubes
Nt =
889.183
19 103 7.22
= 2064
Equation (5.9) is used to calculate the bundle diameter

1
2064 2.207
Db = 19 103 (
)
= 1.133 m
0.249
84
Note that the values of K1 and n1 are obtained from Table 5.2. Next, Figure 5.7 is used to
estimate the clearance required between the outermost tubes in the bundle and the shell inside
diameter. As mentioned previously, a split-ring floating head heat exchanger is selected as it
gives the best performance. The clearance value is equal to 77 mm.
The shell diameter is just the sum of the bundle diameter and clearance. In other words
Ds = 1.133 + 77 103 = 1.21 m
Which is the maximum shell diameter listed by TEMA. As result, a collection of smaller
diameter heat exchangers are connected in parallel to produce the same output temperature.
85
5.2.6 Summary
Table 5.8 E-302 heat exchanger specifications (for one heat exchanger only)
Performance of the Unit
Fluid Allocation
Fluid Name
Total Flowrate
kmol/h
Temp (In/Out)
Inlet Pressure
bar
Heat Load
kW
Overall Coefficient
Shell Side
Tube Side
Water
Water/Acrylic/Acetic
27994.470
38902.320
50
40
2.4
40
1
8782.95
1000.00
889.18
W/m C
Heat Transfer Area
25
Construction Details
Heat Exchanger Type
Split-ring floating head
Number of Passes
Shell (1)
Tube (2)
Tube Dimensions
Outside Diameter
mm
19.00
Inside Diameter
mm
15.60
Thickness
mm
2.70
7.22
Length
Number of Tubes
2064 (1032 per pass)
Material of Constructions
Stainless Steel 318

Shell Dimensions
Bundle Diameter
mm
1133
Clearance
mm
77
Shell Diameter
mm
1210
Pitch Specifications
Type
Spacing
Triangular
mm
23.75
86
5.3
Sizing of Reboiler E-303

Design an acid reboiler, E-303, that is located by the acid tower, T-303, and aims at vaporizing
the acrylic acid in the bottoms stream and send it back to the tower.
5.3.2 Design Considerations

tubes, number of shell and tube passes, pitch type, etc., are listed in Table 5.9.
Internal Component
Specification
Shell Passes
Tube Passes
Tube Thickness
2.1
38
33.8
Tube Length (m)
3.66
Stainless Steel 318
Pitch Type
Square
Pitch Spacing (mm)
47.5
Baffle Type
25%

Liquid Acid Stream (t = 89 C, P = 0.16
bar)
Steam Stream (T = 120.23 C, P = 2 bar)

Gas Acid Stream (t = 89 C, P = 0.16 bar)
E-303
Water Stream (T = 120.23C, P = 2 bar)
Figure 5.13 is a visual representation of the inlet and outlet streams for heat reboiler E-303.
Table 5.10 summarizes the flowrates along with the corresponding temperatures and pressures.
87

Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Phase
Water
Acetic
Acid
Acrylic
Acid
18a
89
0.16
Liquid
0.00
0.09
156.24
18b
89
0.16
Gas
0.00
0.09
156.24
LPS In
120.23
Gas
nw
0.00
0.00
LPS Out
120.23
Liquid
nw
0.00
0.00

In order to carry out design calculations, the physical properties of water and acrylic acid are
needed. These properties include the molecular weight, critical temperature, and latent heat of
vaporization. Table 5.11 lists the properties the saturation temperatures and pressures.
Table 5.11 Physical properties of hot and cold fluids [43]
Property
Acrylic Acid
LPS
Molcular Weight (kg/kmol)
72.063
18
Latent heat of vaporization (kJ/kmol)
46100
39628.62
Critical Temperature (K)
615
647.096
5.3.5 Calculations
The heat load is just the number of moles multiplied by the heat of vaporization.
Q = 156.24 46100 = 7202664 kJ/h
Since no heat losses to the surrounding is assumed, i.e. heat lost by the hot fluid is gained by
nW =
7202664
= 181.75 kmol/h
39628.62
Next we calculate the mean temperature using equation (5.23)

Tm = 120.23 - 89 = 31.23 C
88
The reduced temperature was calculated using equation (5.24)
Tr =
362.15
= 0.588
615
The design heat flux was found from Figure 5.11

q = 25500 W/m2
Calculating the corresponding surface area using equation (5.25)
A=
2000.74 1000
= 78.46 m2
25500
Using Equations 5.26 and 5.27 to calculate the number of tubes and the bundle diameter
Nt =
78.46
33.8 103 3.66
= 201.88 202 Tubes
202 2.207
Db = 38 103 (
)
= 0.845 m
0.215
Figure 5.7 is used to estimate the clearance required between the outermost tubes in the bundle
and the shell inside diameter. The clearance value is equal to 17 mm. The shell diameter is just
the sum of the bundle diameter and clearance. In other words
Ds = 0.845 + 17 103 = 0.862 m
Outlet pipe diameter; take area as equal to total tube cross-sectional area using 5.28
= 202 (33.8 103 )
= 0.1812 m2
4
Then by using equation (5.27), the pipe diameter is evaluated
Pipe diameter =
0.1812 4
= 0.48 m
89
5.3.6 Summary
Table 5.12 E-303 reboiler specifications
Fluid Allocation
Shell Side
Tube Side
Water
Acrylic Acid
kmol/h
181.75
156.24
Temperature
120.23
89
Inlet Pressure
bar
0.16
Heat Load
kW
Fluid Name
Total Flowrate
Heat Flux
2000.74
2
W/m
25500
Heat Transfer Area
78.46
Heat Exchanger Type
Fixed and U-tube
Number of Passes
Shell (1)
Tube (1)
Tube Dimensions
Outside Diameter
mm
38.00
Inside Diameter
mm
33.80
Thickness
mm
2.10
3.66
Length
Number of Tubes
202
Stainless Steel 318

Shell Dimensions
Bundle Diameter
mm
844.93
Clearance
mm
17
Shell Diameter
mm
861.93
Pipe Diameter
mm
480.39
Type
Spacing
Square
mm
47.5
90
5.4
Design of Condenser E-304

Design a condenser for: 359.39 kmol/h of a mixture of acetic acid, acrylic acid, and water is to
be condensed at the same temperature and pressure (P = 0.07 bar and T = 47 o C).
5.4.2 Design Consideration

tubes, number of shell and tube passes, pitch type, etc. These are listed in Table 5.13.
Table 5.13 Internal component specifications of heat exchanger E-304
Internal Component
Specification
Shell Passes
Tube Passes
19
15.6
Tube Length (m)
4.88
Stainless Steel 18/8
Pitch Type
Square
Pitch Spacing (mm)
23.75
Baffle Type
Baffle Spacing
Same as the shell diameter
45%

X (Water) = 0.0473
X (Water) = 0.0473
E-304
91
Figure 5.14 shows the arrangement of inlet and outlet streams for heat exchanger E-304. The
hot stream consists of acetic acid, acrylic acid, and water and is to be condensed at the same
temperature and pressure. Water is used as a coolant with a temperature rise from 25 C to 40
C. Table 5.14 shows a summary of the streams along with the corresponding temperatures and
pressures.
Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Water
Acetic Acid
Acrylic Acid
16
47
0.07
17.01
341.82
0.56
16*
47
0.07
17.01
341.82
0.56
Coolant In
25
1.0
0.00
0.00
Coolant Out
40
1.0
0.00
0.00
(*): Outlet stream of the heat exchanger

In order to carry out design calculations, the physical properties of water and acetic acid are
needed. Some of the properties, such as the latent heat of vaporization and the specific heat
capacity, must be calculated at the average temperature between the inlet and outlet streams.
Therefore,
TAVG =
T1 + T2 47 + 47
=
= 47 C
2
2
tAVG =
t1 + t2 25 + 40
=
= 32.5 C
2
2
And,
Other properties, however, are calculated at the film temperature. Such properties include:
viscosity, density, and thermal conductivity of the shell-side fluid. For these, the values are
listed at two different temperatures to give room for interpolation should we need it. Only those
properties that are needed in design calculations are considered (see Table 5.15).
92
Table 5.15 Physical properties of hot and cold fluids [43]

Property
Value
Acetic Acid Hot Fluid (TAVG = 47 C)
Heat of Vaporization @ TAVG = 47 C
23490 (kJ/kmol)
Molecular Weight
60 (kg/kmol)
Liquid Viscosity (40 C/50 C)
0.9036 (cP)
0.7935 (cP)
Liquid Density (40 C/50 C)
1025 (kg/m3)
1014 (kg/m3)
Liquid Thermal Conductivity (40 C/50 C)
0.1566 (W/m-K)
0.1547 (W/m-K)
Water Cold Fluid (tAVG = 32.5 C)

Molecular Weight
18 (kg/kmol)
Density @ tAVG = 32.5 C
995 (kg/m3)
Liquid Heat Capacity @ tAVG = 32.5 C
75.3 (kJ/kmol-K)
Liquid Viscosity @ tAVG = 32.5 C
0.787 (cP)
Liquid Conductivity @ tAVG = 32.5 C
0.616 (W/m-K)
5.4.4 Calculations
5.4.4.1 Preliminary Calculations (1st Trial)
The heat load is just the number of moles multiplied by the heat of vaporization (condensation)
Q = 341.82 23490 = 8029352 kJ/h
nW =
8029352
kmol
= 7109
75.3(40 25)
h
Next we calculate the mean temperature using Equation 5.2
Tlm =
(47 40) (47 25)

= 13.1 C
47 40
ln (
)
47 25
93
Since condensation occurs at the same temperature, the correction factor is equal to unity.
However, for the sake of argument, let us do the calculations and see whether or not the result
would be the same. Using Equations 5.4
R=
47 47
=0
40 25
Substituting into equation (5.6)
Ft =
1S
0 + 1 ln (1 0 S)
2 S(0 + 1 0 + 1)
(0 1) ln (
)
2 S(0 + 1 + 0 + 1)
ln (1 S)
=1
ln (1 S)
We have confirmed that the correction factor is indeed equal to unity. The mean temperature
is then corrected using equation (5.3)
Tm = 1 13.1 = 13.1 C
The next step is to assume an overall heat transfer coefficient. Everything we have calculated
thus far will not change regardless of how many trials are needed. For a first trial, assume
U = 1000
W
m2 C
homogeneity
A=
8029352 1000
= 170 m2
3600 1000 13.1
Select 15.6 mm inside diameter, 3.4 mm thickness, 4.88 m long tubes, and stainless steel 18/8
for material of construction. Using equation (5.8) to calculate the number of tubes
Nt =
170
19 103 4.88
94
= 585

1
585 2.263
Db = 19 10 (
)
= 0.717 m
0.158
3
Note that the values of K1 and n1 depend on the arrangement of tubes (triangular or square)
and the number of tube passes.
5.4.4.2 Tube-Side Calculations (1st Trial)
As mentioned previously, the physical properties of the tube-side fluid (water) are calculated
at the average temperature of 32.5 C. Table 5.15 gives all the required properties. The molar
flowrate, molecular weight, density, and area of tubes are available and hence the linear
velocity of water can be readily calculated as follows
ut =
n Mw
N
t Ai
2
Where Ai corresponds to the tube cross sectional area and Nt corresponds to the total number
of tubes needed. The total number of tubes is divided by four to account for the selected 1
shell/4 tube pass arrangement. Substituting and making the necessary units conversion
ut =
7109 18
m
= 1.27
2
585
s
3600 995
(15.6 103 )
4
4
Finally, we are able to substitute into the Eagle and Ferguson correlation to calculate the inside
heat transfer coefficient
hi =
4200(1.35 + 0.02 32.5) 1.270.8

3 0.2
(15.6 10 )
= 5878
W
m2 C
5.4.4.3 Shell-Side Calculations (1st Trial)

The condensing coefficient is assumed to be 1500 W/m2 C. Next, the wall temperature is
calculated by using equation (5.18)
95
Tw = 47
1000
(47 32.5) = 37.3 C
1500
The film temperature is just the average between the wall and fluid temperatures
Tf =
47 + 37.3
= 42 C
2
The following liquid physical properties are obtained by interpolating from Table 5.15 at the
film temperature
L = 1023
kg
m3
L = 0.000878 cP
kL = 0.1562
W
mK
The vapor density is calculated from the ideal gas low
V =
PMw
7000 60
kg
=
= 0.16 3
RT
8.314 (273 + 47)
m
Using equation (5.20)
h =
341.82 60
= 0.002
3600 4.88 585
Nr is the average number of tubes in a vertical row. So,
Nr =
2
0.717
= 20
3 19 103 1.25
Now we have everything we need to calculate the condensing coefficient from equation (5.19)
1
1
1023(1023 0.16)9.81 3
W
hc = 0.95 0.1562 [
] 206 = 1621 2
0.000878 0.002
m C
96
Close enough to the assumed value of 1500 and therefore there is no need for further trials
5.4.4.4 Overall Calculations (1st Trial)
In order to check whether the assumed overall heat transfer coefficient is accurate or not,
equation (5.21) is used. The fouling factor hid for water is taken as 3250 W/m2-K and hod for
acetic acid 5000 W/m2-K. The only thing that is missing is the wall thermal conductivity. For
a heat exchanger made of stainless steel 18/8, the thermal conductivity can be taken as
kw = 16
W
m C
Applying equation (5.21)

1
19
19 103 ln (15.6) 19
1
1
1
19
1
W
Uo = [
+
+
+
] = 660 2
1621 5000
2 16
15.6 3250 15.6 5878
m C
5.4.4.5 Preliminary Calculations (2nd Trial)

The previously calculated overall heat transfer coefficient is less than the assumed value. This
indicates that the proposed heat exchanger is under-designed. Therefore, a second trial is
needed.
For the second trial, assume
U = 650
W
m2 C
homogeneity
A=
8029352 1000
= 262 m2
3600 650 13.1
Nt =
262
19 103 4.88
97
= 900

1
900 2.263
Db = 19 10 (
)
= 0.717 m
0.158
3
Since we expect this trial to be accurate, we will use Figure 5.7 to estimate the clearance
required between the outermost tubes in the bundle and the shell inside diameter. A split-ring
floating head heat exchanger is selected as it gives the best performance. The clearance value
is equal to 68 mm.
The shell diameter is just the sum of the bundle diameter and clearance. In other words
Ds = 0.717 + 68 103 = 0.936 m
5.4.4.6 Tube-Side Calculations (2nd Trial)
The linear velocity of water is calculated
ut =
7109 18
m
= 0.83
2
900
s
3600 995
(15.6 103 )
4
4
Substituting into the Eagle and Ferguson correlation, the inside coefficient is equal to
hi =
4200(1.35 + 0.02 32.5) 0.830.8

3 0.2
(15.6 10 )
= 4181
W
m2 C
5.4.4.7 Shell-Side Calculations (2nd Trial)

The condensing coefficient is assumed to be 1800 W/m2 C. The wall temperature is calculated
by using equation (5.18)
Tw = 47
650
(47 32.5) = 41.7 C
1800
The film temperature is just the average between the wall and fluid temperatures
Tf =
47 + 41.7
= 44.4 C
2
98
The following liquid physical properties are obtained by interpolating from Table 5.15 at the
film temperature
L = 1020
kg
m3
L = 0.000853 cP
kL = 0.1558
W
mK
Using equation (5.20)
h =
341.82 60
= 0.0013
3600 4.88 900
Nr is the average number of tubes in a vertical row. So,
Nr =
2
0.868
= 25
3 19 103 1.25
Calculating the condensing coefficient from equation (5.19)

1
1
1020(1020 0.16)9.81 3
W
hc = 0.95 0.1558 [
] 256 = 1815 2
0.000853 0.0013
m C
Close enough to the assumed value of 1800 and therefore there is no need for further trials
5.4.4.8 Overall Calculations (2nd Trial)
Equation (5.21) is used to check the accuracy of the assumed overall coefficient
1
19
19 103 ln (
) 19
1
1
1
19
1
W
15.6
Uo = [
+
+
+
] = 652 2
1815 5000
2 16
15.6 3250 15.6 4181
m C
This value is practically the same as the assumed value of 650. Therefore, this result is
acceptable and no further trials are needed.
99
5.4.4.9 Tube-Side Pressure Drop Calculations

The pressure drop calculations presented here are based on the second trial. Calculating the
Reynolds number using the velocity of water
Re =
995 0.83 15.6 103

= 16394
0.000787
Note that 0.000787 is the viscosity of water at the average temperature.

Using Figure 5.9 to estimate the tube side friction factor
jf = 0.0045
Plugging the numbers into equation (5.17) and neglecting the viscosity term
Pt = 4 (8 0.0045 (
4.88
15.6 10
3 ) + 2.5)
995 0.8312
= 18905 Pa = 18.905 kPa
2
Compared to the tube-side operating pressure of 1000 kPa, a drop of 1.9% is acceptable.
5.4.4.10 Shell-Side Pressure Drop Calculations
In order to calculate the shell-side Reynolds number, we need the effective diameter and the
velocity. For a square pitch arrangement, the effective diameter is calculated as follows
de =
1.27
(0.023752 0.785 0.019) = 0.01876 m
0.019
The area for cross-flow As for hypothetical row of tubes is calculated
As =
(0.02375 0.019) 0.936 0.936

= 0.175 m2
0.02375
The shell-side velocity can now be calculated as follows
us =
341.82 60
m
= 203.44
3600 0.16 0.175
s
100
As mentioned previously, the shell-side pressure drop is taken as 50% that of the pressure drop
at inlet conditions. The Reynolds number is calculated as follows
Re =
0.16 0.01876 203.46

= 66210
0.000009
Note that 0.000009 is the vapor viscosity at the inlet conditions.

Substituting into Figure 5.10 to solve for the shell-side friction factor
jf = 0.025
Substituting into equation (5.22) and neglecting the viscosity term
Ps = [8 0.025 (
0.936
4.88
0.16 203.442
)(
)
] = 85019 Pa = 85.019 kPa
0.01876
0.936
2
Compared to the shell-side pressure of 0.07 bar (7 kPa), a pressure drop of 85.019 kPa is not
accepted. In order to fix this problem, the velocity, must be reduced.
An optimization by reducing the velocity and therefore the pressure drop is vital in this
situation. Otherwise, back flow and blockages might occur.
101
5.4.5 Summary
Table 5.16 E-304 heat exchanger specifications
Fluid Allocation
Fluid Name
Total Flowrate
kmol/h
Temp (In/Out)
Inlet Pressure
bar
Heat Load
kW
Overall Coefficient
Shell Side
Tube Side
Water/Acrylic/Acetic
Water
27994.470
38902.320
47
47
0.07
40
1
2230
650
262
W/m C
Heat Transfer Area
25
Heat Exchanger Type
Number of Passes
Shell: (1)
Tube: (4)
Tube Dimensions
Outside Diameter
mm
19.00
Inside Diameter
mm
15.60
4.88
Length
Number of Tubes
900 (225 per pass)
Stainless Steel 18/8

Shell Dimensions
Bundle Diameter
Mm
868
Clearance
Mm
68
Shell Diameter
Mm
936
Type
Spacing
Square
Mm
23.75
Baffle Specifications
Baffle Type
Baffle Spacing
Baffle Cut
Single segmental baffles

Mm
936
45
102
5.5
Design of Cooler E-305

In the production of acrylic acid, as illustrated in the flowsheet given in Figure 2.1, the product
acrylic acid is recovered from the distillation column, T-303, through the bottom stream
number 18 with a purity of 99.9%, a temperature of 89 C, and pressure of and 2.5 bar. A heat
exchanger E-305 is facilitated afterwards to cool down the product to the allowable handling
temperature of 40 C. The hot product is cooled using a cooling water at 25 C with a maximum
allowable temperature rise to 40 C.
5.5.2 Design Consideration

tubes, number of shell and tube passes, pitch type, etc., are necessary in design calculations.
These are listed in Table 5.17.
Internal Component
Specification
Shell Passes
Tube Passes
Tube Thickness
1.7
19
15.6
Tube Length (m)
4.88
Carbon Steel
Pitch Type
Triangle
Pitch Spacing (mm)
23.75
Baffle Type
Baffle Spacing
Two fifths the shell diameter
25%
103

Before proceeding any forward, the flowrates of the hot fluid and its conditions are recalled
from the material balance and summarized in Table 5.18.
Conditions
Flowrate (kmol/h)
Stream
Temp (C)
Pres (bar)
Total Flow
Acrylic Acid
Acetic Acid
18*
89.00
2.50
156.33
156.24
0.09
18
40.00
2.50
156.33
156.24
0.09
Coolant In
25.00
1.00
0.00
0.00
Coolant Out
40.00
1.00
0.00
0.00
(*): Inlet stream of the heat exchanger
A schematic representation is shown in Figure 5.15

Cold Stream (T = 40 C)
E-305
Cold Stream (T = 25 C)

In order to design the heat exchanger, it is necessary to determine the physical properties of
both the hot and cold fluid in each stream. Such these properties are heat capacity, density
viscosity and thermal conductivity. However, these properties do differ with temperature.
Therefore, it is determined at the arithmetic average value of the inlet and outlet temperature
of each fluid. So the average temperatures are,
Tav =
T1 + T2 89 + 40
=
= 64.50 C
2
2
Tav =
T1 + T2 24 + 40
=
= 32.50 C
2
2
And,
104
All the physical properties are obtained from Yaws Handbook of Thermodynamic and
Chemical Properties of Chemical Compounds [43]. The acrylic acid and water physical
properties are obtained at 64.50 C and 32.50 C and are given in Table 5.19. It should be noted
that, in this context, the effects of acetic acid on the fluids physical properties are negligible.
Table 5.19 Physical properties of the hot and cold fluids
Hot Fluid
Property
Value
Molecular Weight (kg/kmol)
72.000
Density (kg/m3)
1000.266
156.548
Viscosity (mPa.s)
0.600
Conductivity (W/m-K)
0.146
Cold Fluid
Property
Value
Molecular Weight (kg/kmol)
18.000
Density (kg/m3)
994.575
75.297
Viscosity (mPa.s)
0.787
0.616
5.5.5 Calculations
5.5.5.1 Preliminary Calculations (1st Trial)
The heat load is calculated by applying equation (5.1)
Q = (156.33)(156.548)(89.00 - 40.00) = 1199182 kJ/h (333.106 kW)
mC =(75.297)( 40.00 - 25.00 )/(333.106) = 0.295 kmol/s (5.309 kg/s)
105
Next we calculate the mean temperature using equation (5.2)

Tlm = ((89 - 40) - (40 - 25))/ ln((89 - 40)/(40 - 25)) = 28.72 C
Then by applying equations 5.5 and 5.6, R and S are calculated
R=
(89 - 40)
= 3.27
( 40 - 25 )
And,
S=
(40 - 25)
= 0.23
(89 - 25)
Ft =
1 0.23
)
1 3.27 0.23
2 0.23 (3.27 + 1 3.272 + 1)
3.272 + 1 ln (
= 0.831
(3.27 1) ln (
)
2 0.23 (3.27 + 1 + 3.272 + 1)
The mean temperature is then corrected using equation (5.3)

Tm = (0.831) (28.72) = 23.87 C
The next step is to assume an overall heat transfer coefficient. Everything we have calculated
thus far will not change regardless of how many trials are needed. For a first trial, assume
U = 500
W
m2 C
Calculating the corresponding surface area using equation (5.7).
A=
333106
= 27.91 m2
(500)(23.87)
106
Nt =
27.91
19 103 4.88
= 96 Tubes

1
96 2.207
Db = 19 10 (
)
= 0.282 m
0.249
3
Note that the values of K1 and n1 depend on the arrangement of tubes (triangular or square)
and the number of tube passes. From Figure 5.7, clearance is equal to 52 mm for the splitting
head with 0.282 m bundle diameter. The shell diameter Ds is then equal to
Ds = 0.282 + 0.052=0.334 m
5.5.5.2 Tube-Side Calculations (1st Trial)
As mentioned previously, the physical properties of the tube-side fluid (water) are calculated
at the average temperature of 32.5 C. Table 5.19 gives all the required properties. The molar
flowrate, molecular weight, density, and area of tubes are available and hence the linear
velocity of water can be readily calculated as follows
ut =
mC
Nt
Ai
2
Where Ai corresponds to the tube cross sectional area and Nt corresponds to the total number
of tubes needed. The total number of tubes is divided by four to account for the selected 1
shell/2 tube pass arrangement. Substituting and making the necessary units conversion
ut =
5.309
m
= 0.582
2
96
s
994.57
(15.6 103 )
2 4
107
Finally, we are able to substitute into the Eagle and Ferguson correlation to calculate the inside
heat transfer coefficient
hi =
4200 ( 1.35 + 0.02 (32.5) )(0.582)0.8

(15.6)0.2
= 3144 W/m2 Co
5.5.5.3 Shell-Side Calculations (1st Trial)

The baffle spacing is taken to be two fifths the shell diameter, so IB = (0.4)(0.334) = 0.134 m.
Afterwards, the area for cross flow calculated from equation (5.11)
As =
(0.02375 - 0.01900)(0.334)(0.134)
= 0.0089 m2
0.02375
Then the equivalent diameter is calculated using equation (5.12) for triangular pitch.
de =
1.1
(0.023752 - 0.917 (0.0190)2 ) = 0.01349 m
0.019
In order to measure the Reynolds number, the shell velocity is calculated by dividing the
volumetric flowrate (m/) over the cross area available for flow AS
us =
(156.33)(72)/(3600)
= 0.351 m/s
(1000.266)(0.0089)
Applying equation (5.13) to calculate the Reynolds number
Re =
(0.351)(0.01349)(1000.266)
= 7869
(0.0006)
Calculating the Prandtl number
Pr =
Cp (156.548/72000)(0.0006)
=
= 8.97
(0.146)
k
108
For the calculated Reynolds number, jh is read from Figure 5.8 for 25 % baffle cut. The
corresponding value is equal to 0.0064. The shell side heat transfer coefficient hs is then
measured by applying equation (5.14).
hs =
(0.146)
(0.0064)(7869)(8.97)0.33 = 1128.4 W/m2 C
(0.01349)
To get a corrected value of hs, an estimate wall temperature must be made. First, a mean
temperature difference is calculated between the average hot fluid temperature (64.5 C) and
the average cold fluid temperature (32.5 C) as the follows
Toverall = 64.5 - 32.5 = 32 C
Where Toverall is across all the resistances. Since the heat flux is crossing radially (in series),
the following must be applied to measure the temperature difference across the hot fluid film
Tfilm =
U
500
T
=
32 = 14.179 C
hs overall 1128.4
The wall temperature Tw is then equal to

Twall = 64.5 - 14.179 = 50.32 C
The acrylic acid viscosity at the wall temperature is then obtained from Yaws Handbook of
Thermodynamic and Chemical Properties of Chemical Compounds as the following
= 0.728 mpa.s
This gives the following correction
0.600 0.14
hs = (1128.4) (
) = 1098.2805 W/m2 C
0.728
109
5.5.5.4 Overall Calculations (1st Trial)

In order to check whether the assumed overall heat transfer coefficient is accurate or not,
Equation (5.21) is used. The fouling factor hid for water is taken as 3000 W/m2-K and hod for
acrylic acid 5000 W/m2-K. The only thing that is missing is the wall thermal conductivity. For
a heat exchanger made of carbon steel, the thermal conductivity can be taken as
kw = 50
W
m C

1
19
0.019 ln (15.6)
1
1
19
1
19
1
W
Uo = [
+
+
+
] = 516.77 2
1098.2 5000
2 50
15.6 3000 15.6 3144
m C
The overall heat transfer coefficient calculated is above the assumed value by 3.354%. This is
considered acceptable.
5.5.5.5 Preliminary Calculations (2nd Trial)
For more accurate calculations, a second trial is recommended. For the second trial, assume
U = 520
W
m2 C
homogeneity
A=
333106
= 26.84 m2
(520)(23.87)
Nt =
26.84
19 103 4.88
110
= 93 Tubes

1
93 2.207
Db = 19 10 (
)
= 0.278 m
0.249
3
Since we expect this trial to be accurate, we will use Figure 5.7 to estimate the clearance
required between the outermost tubes in the bundle and the shell inside diameter. A split-ring
floating head heat exchanger is selected as it gives the best performance. The clearance value
is equal to 51.9 mm. The shell diameter is just the sum of the bundle diameter and clearance.
In other words
Ds = 0.278 + 0.0519 = 0.330 m
5.5.5.6 Tube-Side Calculations (2nd Trial)
The linear velocity of water is calculated
ut =
5.309
m
= 0.594
2
94
s
994.57 2 4 (15.6 103 )
We have used 47 tubes per pass which is shown in a number of 94 instead of the calculated 93.
Then by substituting into the Eagle and Ferguson correlation, the inside coefficient is equal to
hi =
4200(1.35 + 0.02 (32.5))(0.594)0.8

(15.6)0.2
= 3197.29 W/m2 C
5.5.5.7 Shell-Side Calculations (2nd Trial)

The baffle spacing is taken as two fifths the shell diameter, so IB = (0.4)(0.330) = 0.132 m.
Afterwards, the area for cross flow calculated by equation (5.11)
As =
(0.02375 - 0.01900) (0.330) (0.132)

= 0.00871 m2
0.02375
111
The shell velocity is calculated in the same manner given in the first trial
us =
(156.33)(72) / (3600)
= 0.359 m/s
(1000.266)(0.00871)
Applying equation (5.13) to calculate the Reynolds number
Re =
(0.359)(0.01349)(1000.266)
= 8067
(0.0006)
For the calculated Reynolds number, jh is again read from Figure 5.8 and is equal to 0.0063.
The shell side heat transfer coefficient hs is then measured by applying equation (5.14)
hs =
(0.146)
(0.0063)(8067)(8.97)0.33 = 1138.76 W/m2 C
(0.01349)
To get a corrected value of hs, an estimate wall temperature must be made in the same manner
shown in the first trial.
Tfilm =
500
32 = 14.612 C
1138.76
The wall temperature Tw is equal to,

Twall = 64.5 - 14.612 = 49.89 C
The acrylic acid viscosity at the wall temperature is obtained as = 0.7324 mpa.s. The
corrected value can now be calculated
0.600 0.14
hs = (1128.4) (
) = 1107.4126 W/m2 C
0.7324
5.5.5.8 Overall Calculations (2nd Trial)
Equation (5.21) is used to check the accuracy of the assumed overall coefficient
1
19
0.019 ln (15.6)
1
1
19
1
19
1
W
Uo = [
+
+
+
] = 520.52 2
1107.4 5000
2 50
15.6 3000 15.6 3197.3
m C
112
This value is practically the same as the assumed value of 520. Therefore, this result is very
accurate and no further trials are needed.
5.5.5.9 Tube-Side Pressure Drop Calculations
The pressure drop calculations presented here are based on the second trial. Calculating the
Reynolds number using the velocity of water
Re =
(0.594)(0.0156)(994.575)
= 11721
(0.0007865)
Using Figure 5.9 to estimate the tube side friction factor

jf = 0.0047
Plugging in the numbers into equation (5.17) and neglecting the viscosity term
4.88
994.575 (0.594)2
Pt = 2 [8 (0.0047) (
) + 2.5]
= 5008 Pa (5 kPa)
0.0156
2
Which is considered a low pressure drop. Therefore, an increase in the number of passes might
be considered in the optimization process.
5.5.5.10 Shell-Side Pressure Drop Calculations
In order to measure the shell side pressure drop, shell linear velocity must be first calculated.
The Reynolds number has already been calculated in the first trial and is equal to 8067.
Substituting into Figure 5.10 to solve for the shell-side friction factor
jf = 0.05
Substituting into equation (5.22) and neglecting the viscosity term
Ps = 8 (0.05) (
0.330
4.88 1000.27 (0.359)2
)(
)(
) = 23318 pa (23.3 kPa)
0.01349 0.132
2
Which is considered acceptable
113
5.5.6 Summary
Table 5.20 E-305 heat exchanger specifications
Fluid Allocation
Fluid Name
Total Flowrate
kg/s
Temp (In/Out)
Inlet Pressure
Bar
Heat Load
kW
Overall Coefficient
Shell Side
Tube Side
Acrylic Acid
Water
3.13
5.309
47
47
25
2.5
1
303.106
520.00
26.84
W/m C
Heat Transfer Area
40
Heat Exchanger Type
Number of Passes
Shell: (1)
Tube: (2)
Tube Dimensions
Outside Diameter
mm
19.00
Inside Diameter
mm
15.60
4.88
Length
Number of Tubes
94 (47 per pass)
Carbon Steel
Shell Dimensions
Bundle Diameter
mm
278.1
Clearance
mm
51.9
Shell Diameter
mm
330.0
Type
Spacing
Square
mm
23.75
Baffle Specifications
Baffle Type
Baffle Spacing
Baffle Cut
Single segmental baffles

mm
132
25
114
Part Two
Distillation Columns
115
5.6
Background of Distillation Columns
5.6.1 Definition
Distillation is a process in which a liquid or vapor mixture of two or more substances is
separated into its component fractions of desired purity, by the application and removal of heat.
Distillation may result in essentially complete separation (nearly pure components), or it may
be a partial separation that increases the concentration of selected components of the mixture.
In either case the process exploits differences in the volatility of mixture's components [32].
5.6.2 Main Components of a Distillation Column

Distillation columns are made up of several components, each of which is used either to transfer
heat energy or enhance mass transfer. A typical distillation contains several major components:
A vertical shell where the separation is carried out
Trays/plates and/or packings that are used to enhance the separation
A reboiler to provide the necessary vaporization for the distillation process
A condenser to cool and condense the vapor leaving the top of the column
A reflux drum to hold the condensed vapor so that it can be recycled back to the column
Each component will be carefully designed for the distillation column of the acrylic acid plant
5.6.3 Basic Operation

The liquid mixture that is to be processed is known as the feed and this is introduced usually
somewhere near the middle of the column to a tray known as the feed tray. The feed tray divides
the column into a top (enriching or rectification) section and a bottom (stripping) section. The
feed flows down the column where it is collected at the bottom in the reboiler [33].
Heat is supplied to the reboiler to generate vapor. The source of heat input can be any suitable
fluid, although in most chemical plants this is normally steam. In refineries, the heating source
may be the output streams of other columns. The vapor raised in the reboiler is re-introduced
into the unit at the bottom of the column. The liquid removed from the reboiler is known as the
bottom product [33].
116
The vapor moves up the column, and as it exits the top of the unit, it is cooled by a condenser.
The condensed liquid is stored in the reflux drum. Some of this liquid is recycled back to the
column and this is called the reflux. The condensed liquid that is removed from the system is
known as the distillate or top product.
5.6.4 Reflux
Reflux is a distillation technique involving the condensation of vapors and the return of this
condensate to the system from which it originated. It is used in industrial and laboratory
distillations. It is also used in chemistry to supply energy to reactions over a long period of
time [35].
Figure 5.16 The reflux system in a typical distillation column
Referring to Figure 5.61, the downflowing reflux liquid provides cooling and partial
condensation of the upflowing vapors, thereby increasing the efficiency of the distillation
tower. The more reflux that is provided, the better is the tower's separation of the lower boiling
from the higher boiling components of the feed.
117
5.6.5 Types of Columns

There are two of columns in operation: batch and continuous columns
5.6.5.1 Batch Columns
In batch operation, the feed to the column is introduced batch-wise. That is, the column is
charged with a batch and then the distillation process is carried out. When the desired task is
achieved, a next batch of feed is introduced [32].
The simplest and most frequently used batch distillation configuration is the batch rectifier,
shown in Figure 5.17, including the alembic and pot still. The batch rectifier consists of a pot
(or reboiler), rectifying column, a condenser, some means of splitting off a portion of the
condensed vapor (distillate) as reflux, and one or more receivers.
Figure 5.17 Diagram of a batch rectifier
The pot is filled with liquid mixture and heated. Vapor flows upwards in the rectifying column
and condenses at the top. Usually, the entire condensate is initially returned to the column as
reflux. This contacting of vapor and liquid considerably improves the separation. Generally,
this step is named start-up [35]. The first condensate is the head, and it contains undesirable
components. The last condensate is the feints and it is also undesirable, although it adds flavor.
In between is the heart and this forms the desired product.
118
5.6.5.2 Continuous Columns

Continuous columns process a continuous feed stream. No interruptions occur unless there is
a problem with the column or surrounding process units. They are capable of handling high
throughputs and are the more common of the two types [32].
Continuous distillation differs from batch distillation in the respect that concentrations should
not change over time. Continuous distillation can be run at a steady state for an arbitrary amount
of time. For any source material of specific composition, the main variables that affect the
purity of products in continuous distillation are the reflux ratio and the number of theoretical
equilibrium stages (practically, the number of trays or the height of packing).
Continuous distillation is used widely in the chemical process industries where large quantities
of liquids have to be distilled. Such industries are the natural gas processing, petrochemical
production, coal tar processing, liquor production, hydrocarbon solvents production and similar
industries, but it finds its widest application in petroleum refineries [36].
5.6.6 Types of Trays

The terms trays and plates are used interchangeably. There are many types of tray designs, but
the following are the most common ones:
5.6.6.1 Bubble Cap Trays
A bubble cap tray, shown in Figure 5.18, has riser or chimney fitted over each hole, and a cap
that covers the riser. The cap is mounted so that there is a space between riser and cap to allow
the passage of vapor. Vapor rises through the chimney and is directed downward by the cap,
finally discharging through slots in the cap, and finally bubbling through the liquid on the tray.
Bubble cap trays are best suited for applications with low liquid flows [32].
Figure 5.18 Bubble cap tray
119
5.6.6.2 Valve Trays

In valve trays, as shown in Figure 5.19, perforations are covered by liftable caps. Vapor flows
lift the caps thus self-creating a flow area for the passage of vapor. The lifting cap directs the
vapor to flow horizontally into the liquid, thus providing better mixing than is possible in sieve
trays.
Figure 5.19 Valve tray
5.6.6.3 Sieve Trays

Sieve trays, as shown in Figure 5.20, are simply metal plates with holes in them. Vapor passes
straight upward through the liquid on the plate. The arrangement, number and size of the holes
are design parameters. Because of their efficiency, wide operating range, ease of maintenance
and cost factors, sieve and valve trays have replaced the once highly thought of bubble cap
trays in many applications [33].
Figure 5.20 Sieve tray
5.6.7 Applications of Distillation

Commercially, distillation has many applications. The following are a few examples
Separation of air into its components for industrial use.
In the fossil fuel industry for obtaining materials from crude oil.
Recovering ethanol/acetone from manufacturing effluent.
Purification of raw alcohol.
120
5.7
Design of Distillation Column T-303

Design a distillation column that has the composition given in the table below, and is at a
pressure of 0.19 bar and a temperature of 90 C.
Table 5.21 Distillation column T-303 flowrates
Species
Feed (kmol/h)
Distillate (kmol/h)
Bottoms (kmol/h)
Water
0.54
0.54
0.00
Acetic Acid
10.94
10.85
0.09
Acrylic Acid
156.26
0.02
156.24
5.7.2 Composition
The molar composition of the tower inlet and outlets are given in Table 5.22. Note that during
the remaining discussion, the notations XF, XD, and XW, will represent the molar flowrate of
the light component (i.e. acetic acid) at the feed, distillate, and bottoms, respectively.
Table 5.22 Distillation column T-303 compositions
Species
Feed
Distillate
Bottoms
Water
0.003219
0.047327
0.000000
Acetic Acid
0.065220
0.950920
0.000576
Acrylic Acid
0.931561
0.001753
0.999424
Figure 5.21 is a visual representation of the information given in Tables 5.21 and 5.22
17 (After pump)
T = 47.00 C, P = 1.10 bar
X (Water) = 0.047327
T = 90.00 C, P = 0.19 bar

X (Water) = 0.003219
T-303
15
T = 89.00 C, P = 0.16 bar
X (Water) = 0.000000
N/A (Before pump)

Figure 5.21 Visual representation of the inlet and outlet streams for distillation column T-303
121
5.7.3 Assumptions
In order to design the required distillation column, the following assumptions are made
Assume a binary mixture (water is available in negligible amounts)
The negligible amount of water is added to the light component
Assume constant molal overflow
Assume the operating pressure is the average between the top and bottom
Any missing data that are not considered here will be assumed in the calculations.
5.7.4 Stage Equilibrium Relations

It is assumed in a distillation column that any two streams exiting a stage are in equilibrium
with each other and therefore it is essential to provide a relationship between these two streams.
A thermodynamic model called Raoults law gives a solution to this problem. It gives a
relationship between the mole fractions of two phases in equilibrium with each other. It
assumes ideal behavior based on the simple microscopic assumption that intermolecular forces
between unlike molecules are equal to those between similar molecules; which apply for the
mixture of water, acrylic acid, and acetic acid. It is defined as
pi = p*i Xi
(5.29)
Where pi is the partial pressure of the ith component in the vapor phase, p*i the vapor pressure,
and Xi the mole fraction in the liquid phase. If we divide both sides of equation (5.29) by the
total pressure P, we obtain the following
Yi =
p*i
X
P i
(5.30)
By applying Raoults law simultaneously with Dalton's law which states that the total
pressure is equal to the sum of the partial pressures we can relate the liquid and vapor fraction
of the binary mixture of acrylic acid and acetic acid as the follows
XAcetic Acid =
P - p*Acrylic Acid
*
pAcetic Acid - p*Acrylic Acid
122
(5.31)
The corresponding vapor composition is obtained from equation (5.30)
YAcetic Acid =
p*Acetic Acid
P
XAcetic Acid
(5.32)
Usually, the total pressure P is known or given, and the calculation of the vapor pressure pi at
a certain temperature is needed. To do so, the Antoine equation is used
B
p*i (mmHg) = 10 A - C + T
(5.33)
Where p*i is the vapor pressure to be substituted into equations (5.31) and (5.32), and A, B, and
C are component specific parameters. Table 5.23 gives the values of these parameters for the
three components involved in this distillation unit.
Table 5.23 Constants A, B and C to be used with equation (5.33)
Species
Acrylic Acid
7.82557
1817.73000
226.60900
Acetic Acid
7.81520
1800.03000
246.89400
As mentioned previously, the total operating pressure P will be taken as the average between
the top and bottom of the column. Going back to Figure 5.21, we see that the pressure of the
top stream is given after the pump. The pressure before pumping would be that of stream 16
and is equal to 0.07 bar. The pressure of the bottom stream is given before the pump and is
equal to 0.16 bar. Therefore, the column operating pressure is
P=
0.07 + 0.16
= 0.115 bar = 86.257 mmHg
2
Note that the values given in Table 5.23 give the vapor pressure in mmHg units and therefore
the operating pressure was converted to mmHg. Now we have everything we need to apply
equations (5.31) and (5.32) at various points down the column. By doing so we obtain what is
called an equilibrium curve that relates the compositions of the liquid and vapor phases.
Table 5.24 summarizes the calculations.
123
Table 5.24 Column measurements

Temp (C)
p*Acetic Acid
p*Acrylic Acid
XAcetic Acid
YAcetic Acid
Eq. (5.33)
Eq. (5.33)
Eq. (5.31)
Eq. (5.32)
59.2645
86.2570
86.2570
29.3129
1.0000
1.0000
62.5147
86.2570
99.4384
34.5571
0.7968
0.9186
65.7648
86.2570
114.2957
40.5907
0.6196
0.8210
69.0150
86.2570
130.9971
47.5094
0.4641
0.7048
72.2652
86.2570
149.7224
55.4174
0.3270
0.5676
75.5153
86.2570
170.6640
64.4278
0.2055
0.4065
78.7655
86.2570
194.0271
74.6635
0.0971
0.2185
82.0157
86.2570
220.0298
86.2570
0.0000
0.0000
We have employed the Antoine equation in obtaining the equilibrium relationship. A visual
representation of the TXY diagram is given in Figure 5.22. Note that the composition is for
acetic acid, and since we assumed a binary mixture, the remaining would be for acrylic acid.
T-X-Y Diagram
85
Temperature (C)
80
75
70
65
60
55
50
0
0.1
0.2
0.3
0.4
0.5
0.6
X, Y (Acetic Acid)
Figure 5.22 T-X-Y diagram plot
124
0.7
0.8
0.9
It is also necessary to show the relationship between X and Y at equilibrium (see Figure 5.23).
This relationship is plotted using the mole fraction in the liquid and vapor phases given in Table
4. The 45 line is also plotted to show the reader that the equilibrium line lies above the 45
line which means that separation is possible.
X-Y Diagram
1
0.9
0.8
Y (Acetic Acid)
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
X (Acetic Acid)
Figure 5.23 X-Y diagram plot
5.7.5 McCabe-Thiele Method

McCabe-Thiele Method is a mathematical-graphical method for determining the theoretical
number of stages needed for a separation of a binary mixture. The main assumption of this
method is that there must be equimolar overflow through the tower between the feed inlet and
the top of the tower and the feed inlet and bottom tray.
5.7.5.1 Equations for Enriching Section
The upper part of the tower above the feed entrance is called the enriching section. Since
equimolar over flow is assumed, L1 = L2 = Ln and V1 = V2 = Vn = Vn+1. Making a total material
balance over the dashed-line section shown in Figure 5.24:
Vn+1 = Ln + D
125
(5.34)
Making a component balance and solving for yn+1

Yn+1 =
Ln
DXD
X +
Vn+1 n Vn+1
(5.35)
Define the reflux ratio R = Ln /D and substitute into the previous equation
Yn+1 =
R
XD
X +
R+1 n R+1
(5.36)
Figure 5.24 Enriching section
The previous equation is a straight line on a plot of the vapor composition versus the liquid
composition. It relates the composition of two streams passing each other. It intersects the 45
diagonal line at X = XD. The theoretical stages are determined by starting at XD .
5.7.5.2 Equations for Stripping Section
The lower part of the tower below the feed entrance is called the stripping section. By making
a material balance around the dashed-line section (see Figure 5.25) and following the same
steps as before we obtain the stripping-section operating line
Ym+1 =
Lm
WXw
X +
Vm+1 m Vm+1
126
(5.37)
Figure 5.25 Stripping section
The previous equation is a straight line on a plot of the vapor composition versus the liquid
composition. It relates the composition of two streams passing each other. It intersects the 45
diagonal line at X = Xw. The theoretical stages are determined by starting at Xw and going up
to Yw .
5.7.5.3 Determination of the Minimum Reflux Ratio R m
The reflux ratio can be determined from the following equation
Rm
X D - Y'
=
Rm + 1 XD - X'
(5.38)
Where Y' and X' are the intersection of the q-line with the equilibrium curve. The minimum
reflux is usually calculated to estimate an optimum value for the operating reflux. The reflux
ratio affects both the number of trays and the height of the tower. Therefore, an economic
balance between the two is required. It has been shown in many cases that an operating reflux
ratio between 1.2Rm and 1.5Rm provides the lowest total cost, where Rm is defined as the reflux
ratio that will require an infinite number of plates for a desired separation. For this design,
however, we will not improvise. Instead, we will use the same reflux ratio set by the designer
(given in the material balance calculations).
127
5.7.5.4 Determination of Theoretical Number of Trays

To determine the theoretical number of stages, the enriching and stripping lines are plotted to
intersect on the q-line. The equilibrium, enriching, stripping, and q lines are shown in Figure
5.26
Figure 5.26 Location of the q-line for various feed conditions
The value of q can be calculated using the following equation
q=
(HV - HF )
(HV - HL)
(5.39)
Where HV is the enthalpy of the feed at the dew point and HL the enthalpy of the feed at the
bubble point. For a liquid below boiling point, (q > 1), liquid at boiling point, (q = 1), liquid +
vapor (0 < q < 1), and for saturated vapor (q = 0).
The steps are determined by starting at XD and stepping off the first plate to cut the equilibrium
line at X1. Y2 is then determined by applying the operating line at X1 (step down to the operating
line).
128
5.7.5.5 Determination of the Minimum Number of Trays

The minimum number of trays can be calculated with the help of the total reflux concept (i.e.
R ). When an infinite reflux ratio is used, a minimum number of trays Nm is obtained. This
is illustrated graphically by realizing that the slope of the lines become equal to one, or in other
words:
Y=X
(5.40)
This is essentially the 45 line equation, and thus the number of stages are obtained graphically
in the same manner described in section 5.7.5.4, with the exception of using the 45 line in
place of the stripping and enriching lines.
5.7.6 Calculations
5.7.6.1 Theoretical Number of Stages
As mentioned previously, the operating reflux will be taken from material balance calculations
R = L / D = (V D) / D = (359.39 11.41) / (11.41) = 30.5
Note that the negligible amount of water was added to acetic acid, thus
XD = 0.047327 + 0.950920 = 0.998247
The enriching line is then calculated from equation (5.36)
Yn+1 =
30.5
0.998247
X +
30.5 + 1 n 30.5 + 1
Simplifying
Yn+1 = 0.9680Xn + 0.0317
By applying equations (5.31) and (5.33) at the inlet pressure of 0.19 bar, we obtain a saturation
temperature of 90 C. This is indeed the same temperature of the feed, which indicates that the
feed enters the tower as a saturated liquid. Equation (5.39) reduces to
q=
(HV - HF ) (HV - HL )
=
=1
(HV - HL ) (HV - HL )
129
The q-line is therefore drawn vertically and intersects the x-axis at:
XF = 0.003219 + 0.065220 = 0.068439
Again, the composition XF is assumed to be for water and acetic acid. Finally, the stripping
line is drawn between the intersection of the q-line and the enriching line, and the intersection
of the 45 line at XW = 0.000576. The theoretical number of stages are now calculated
graphically in the manner described previously. The results are plotted in Figure 5.27.
Theoretical Number of Stages

1
0.9
0.8
Y (Acetic Acid)
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
X (Acetic Acid)
Figure 5.27 Theoretical number of stages graphical determination
Approximately 17 stages are needed (16 trays + 1 reboiler). The feed tray is obtained by
stepping off the q-line. This occurs at about the ninth stage. Thus,
Feed plate = 9th plate from the top
5.7.6.2 Minimum Reflux Ratio Rm
From Figure 5.27, we can see that the q-line intersect the equilibrium line at:
Y' = 0.160000 X' = 0.068439
130
By applying equation (5.38)

Rm
0.998247 - 0.160000
=
= 0.90153
Rm + 1 0.998247 - 0.068439
Solving for Rm , we obtain the following
Rm = 9.09
If we were to multiply Rm by a factor to obtain the operating reflux ratio of 30.5, it would be
3.355Rm = 30.5 = Operating reflux ratio
The operating reflux clearly does not follow our previous assertion that the best conditions lie
between 1.2Rm and 1.5Rm. The operating reflux ratio of 3.355Rm is governed by mass balance
calculations. All subsequent calculations will be based on the mass balance reflux ratio.
5.7.6.3 Minimum Number of Stages
As mentioned previously, the minimum number of stages can be obtained graphically by
plotting the equilibrium and 45 lines. Figure 5.28 summarizes the results.
Minimum Number of Stages

1
0.9
Y (Acetic Acid)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
X (Acetic Acid)
Figure 5.28 Minimum number of stages graphical determination
131
0.9
1.0
The minimum number of stages are therefore

Nm = 13.5 stages
The minimum number of stages can also be obtained analytically using the following Fenske
formula
XD
1-X
log (1 - X
X W)
D
W
Nm =
log(AVG )
(5.41)
Where AVG is the geometric average volatility between the top and bottom of the tower.
Calculating the volatility at the top of the tower from the data given in Table 5.24
TOP =
86.2570
= 2.9426
29.3129
And at the bottom of the tower,
Bottom =
220.0298
= 2.5508
86.2570
The geometric average is therefore

AVG = 2.9426 2.5508 = 2.7397
Nm =
0.998247
1 - 0.000576
log (
)
1 - 0.998247
0.000576
= 13.69
log(2.7397)
This is fairly close to the graphical value of 13.5 stages
132
5.7.6.4 Actual Number of Stages

In the previous analysis, we have assumed that the vapor leaving each plate was in equilibrium
with the liquid leaving the same plate. This analysis assumed that plates are operating at 100%
efficiency. However, in actual practice, the plates are not perfect, i.e. there are deviations from
ideal conditions.
Except when temperature changes significantly (for example, in presence of exothermic
chemical reaction) from plate to plate, the assumption that vapor and liquid leaving the plates
are at the same temperature is often reasonable. The equilibrium with respect to mass transfer,
however, is not often valid. This can be due to insufficient time of contact or insufficient degree
of mixing.
Therefore in actual operation the vapor and liquid streams leaving a plate are not in equilibrium.
To achieve the same degree of separation, more plates must be added to compensate for the
lack of perfect separation. The actual number of plates required can be adjusted using the tray
efficiency. We define the overall column efficiency EO as follows
EO =
No. of theoretical plates

No. of actual plates
(5.42)
EO is applied throughout the whole column, i.e. every plate is assumed to have the same
efficiency. The advantage is that it is simple to use, but it must be bear in mind that in actual
practice, not all the plates have the same efficiency. Values of EO can be predicted using the
OConnell correlation
EO = 51 - 32.5 log(AVG AVG )
(5.43)
The overall column efficiency is correlated with the product of the relative volatility of the
light key (relative to the heavy key) and the molar average viscosity of the feed, estimated at
the average column temperature. The correlation was based mainly on data obtained with
hydrocarbon systems. The method takes no account of the plate design parameters, and
includes only two physical property variables.
133
The following correlation is obtained from Yaws Handbook of Thermodynamic and Chemical
Properties of Chemical Compounds and will be used for the estimation of liquid viscosity
= 10(A + B/T + CT + DT
(5.44)
Where the liquid viscosity is in cP and the temperature T is in K. Values of constants A, B,

C, and D are given in Table 5.25.
Table 5.25 Constants to be used with equation (5.44)
Species
Acrylic Acid
-1.5418E+01
2.3541E+03
3.3600E-02
-2.7354E-05
Acetic Acid
-3.8937E+00
7.8482E+02
6.7000E-03
-7.5606E-06
The viscosity is calculated at the average temperature of the column, hence
TAVG =
59.2645 + 82.0157
= 76.6401 C = 343.7901 K
2
The viscosity of the two components is calculated at the average temperature by using equation
(5.44). The final results are as follows
(Acrylic Acid) = 0.559 cP
(Acetic Acid) = 0.629 cP
Calculating the molar average viscosity using the feed compositions given in Table 5.22
AVG = 0.931561 0.559 + 0.068439 0.629 = 0.564 cP
EO = 51 - 32.5 log(0.564 2.7397) = 44.85 %
Note that the average volatility is obtained from previous calculations. The actual number of
plates is now calculated from equation (5.42) as follows
134
No. of actual plates =
No. of theoretical plates

16
=
= 35.67
EO
0.4485
In practice, the number of plates must be an integer. By rounding off, we obtain 36 plates.
5.7.6.5 Tower Height
The height of a distillation column is calculated by multiplying the number of actual trays by
the tray separation. Tray spacing can be determined as a cost optimum, but is usually set by
mechanical factors. The most common tray spacing is 0.6 meters it prevents flooding and
allows workers to crawl inside whenever maintenance is needed.
In addition to the space occupied by the trays, height is needed at the top and bottom of the
column. Space at the top typically an additional 1.5 to 3.0 meters is needed to allow for
disengaging space.
From previous calculations, the actual number of trays = 36 and hence there are 35 spaces inbetween. Add to that top and bottom disengaging space and we obtain the following
Tower height = 35 spaces 0.6 m + 1.5 m (top) + 1.5 m (bottom) = 24 m
5.7.6.6 Tower Diameter
The flooding condition fixes the upper limit of vapor velocity. A high vapor velocity is needed
for high plate efficiencies. The operating velocity is usually between 70 and 90% of that which
would cause flooding. For this design, a value of 80% of the flooding velocity will be used.
The flooding velocity can be estimated from the correlation given by Fair
-
uf = K1 L v
v
(5.45)
K1 is a constant obtained from Figure 9. The x-axis is defined by
FLV =
Lw
v
Vw L
135
(5.46)
Where Lw and Vw are the liquid and vapor molar flowrates, respectively.
Figure 5.29 Fair correlation for calculating the flooding velocity
Since the vapor and liquid flowrates vary throughout the column, a diameter calculation should
be for several points up the column. It is usually sufficient to design for the conditions above
and below the feed plate. Different column diameters would only be used when there is a
considerable change in flowrate. The total flowrate of the feed, distillate and bottoms is given
in Table 5.21.
F = 167.74 kmol/h, D = 11.41 kmol/h, B = 156.33 kmol/h
The liquid amount above the feed plate is calculated as
LAbove = R D = 30.5 11.41 = 348.005 kmol/h
The liquid amount below the feed plate is calculated previously as well
LBelow = R D + F = 30.5 11.41 + 167.74 = 515.745 kmol/h
The vapor flowrate below and above the feed plate is approximately constant. So,
V = D(1 + R) = 11.41(1 + 30.5) = 359.415 kmol/h
136
To simplify calculations, the top of the column will be assumed to consist only of acetic acid.
This is a reasonable assumption since acetic acid represents 95 mol% of the distillate. The
following are the physical properties of acetic acid at the top temperature of 47 C
Table 5.26 Physical properties of acetic acid at 47 C
Property
Value
Vapor density (kg/m3)
0.158
Liquid density (kg/m3)
1017.567
Molecular weight (kg/kmol)
60.000
Surface tension (N/m)
0.025
Likewise, assuming that the bottom consists only of acrylic and obtaining the corresponding
physical properties at the temperature of 89 C
Table 5.27 Physical properties of acrylic acid at 89 C
Property
Value
Vapor density (kg/m3)
0.383
969.379
72.000
0.022
We now use equation (5.46) to calculate the factor FLV for conditions above and below the feed
FLV (Above) =
348.005
0.158
= 0.01206
359.415
1017.567
FLV (Below) =
515.745
0.383
= 0.02852
359.415
969.379
We use Figure 5.29 to obtain the value of K1. Note that the assumed tray spacing was 0.6 m
K1 (Above) = 0.10
137
K1 (Below) = 0.12
These values of K1 apply to nonfoaming systems and trays meeting certain hole and weir size
restrictions. It will need to be corrected for surface tension as follows
0.025 0.2
K1 (Above) = 0.10 (
) = 0.1045
0.02
0.022 0.2
K1 (Below) = 0.12 (
) = 0.1223
0.02
Using equation (5.45) to calculate the flooding velocity for both conditions
1017.567 - 0.158
uf (Above) = 0.1045
= 8.39 m/s
0.158
969.379 - 0.383
uf (Below) = 0.1223
= 6.15 m/s
0.383
As mentioned previously, an operating velocity of 80% the flooding velocity is acceptable. So,
uf (Above) = 8.39 0.8 = 6.71 m/s
uf (Below) = 6.15 0.8 = 4.92 m/s
Calculating the maximum volumetric flowrate at the top and bottom conditions
v (Above) =
359.415 60
= 37.9 m3 /s
3600 0.158
v (Below) =
359.415 72
= 18.8 m3 /s
3600 0.383
Calculating the net required area by dividing the maximum volumetric flowrate by the
corresponding operating velocity
A (Above) =
37.9
= 5.648 m2
6.71
138
A (Below) =
18.8
= 3.813 m2
4.92
The downcomer area is usually 12% the total area. The column cross sectional area is therefore,
Cross-Sectional Area (Above) =
5.648
= 6.418 m2
0.88
Cross-Sectional Area (Below) =
3.813
= 4.333 m2
0.88
Calculating the diameter for both conditions
4 6.418
D (Above) =
= 2.859 m
4 4.333
D (Below) =
= 2.349 m
As mentioned previously, there is no need to use different diameters along the length of the
column. The largest diameter, which is for conditions above the feed plate, will be taken.
5.7.6.7 Tray Selection
Bubble-cap trays will be used due to the advantage of having risers that maintain the liquid on
the tray at all vapor flowrates. The trays are made from 18/8 stainless steel (SAE 304) as it has
a higher corrosion resistance.
5.7.6.8 Tower Material of Construction (MOC)
The column vessel will be made from carbon steel. The only problem with using carbon steel
is corrosion. To solve this issue, the vessel will be coated with a thin layer of the superior 18/8
stainless steel (SAE 304).
139
5.7.7 Summary
Table 5.28 T-303 distillation column specifications
Feed Composition
XWater = 0.003219
XAcrylic = 0.931561
XAcetic = 0.065220
Distillate Composition
XWater = 0.047327
XAcrylic = 0.001753
XAcetic = 0.950920
Bottoms Composition
XWater = 0.000000
XAcrylic = 0.999424
XAcetic = 0.000576
Feed Condition
Saturated liquid (T = 90.00 C, P = 0.19 bar)
Inlet Flowrate
kmol/h
167.74
Distillate Flowrate
kmol/h
11.41
Bottoms Flowrate
kmol/h
156.33
Operating Pressure
bar
0.115
Reflux Ratio
30.5
Minimum Reflux
9.09
Efficiency
44.85%
Dew/Bubble Temp
47
89
Flooding Velocity
m/s
Above feed = 8.39
Below Feed = 6.15
Operating Velocity
m/s
80% of flooding velocity

Number of Actual Trays
36
Feed Tray
9 (from the top)
Tray Type
Bubble-cap
Tray Spacing
0.6
Top/Bottom Space
Height
24
Diameter
2.859
Downcomer Area
m2
12% of the total cross sectional area
1.5
1.5
Column MOC
Carbon steel with 318 stainless steel coating
Trays MOC
318 stainless steel
140
5.8
Design of Absorption Column T-302

Design a tray absorption tower that absorbs acetic acid and acrylic acid from a mixture of
propylene, oxygen, nitrogen, carbon dioxide, water, acetic acid, and acrylic acid. The vapor
stream fed to the tower contains 2.00 and 14.35 kmol/h of acetic acid and acrylic acid,
respectively, and an amount equal to 1.17 and 12.58 kmol/h, respectively, is to be recovered.
Pure water (solvent) enters the tower at 25.00 C and 5.00 bar.
5.8.2 Flowrate of Inlet and Outlet Streams

The molar flowrate of the tower inlet and outlet streams as well as temperatures and pressures
are given in Table 5.29.
Table 5.29 Tray absorption tower T-302 flowrates
Properties
Flowrate (kmol/h)
Stream
T (C)
P (bar)
C3H6
N2
O2
CO2
H2O
Acetic
Acrylic
12
25.00
5.00
0.00
0.00
0.00
0.00
253.80
0.00
0.00
11
48.00
1.00
26.46
1902.06
93.42
108.90
270.36
0.83
1.76
63.00
2.00
0.00
0.00
0.00
0.00
253.62
1.17
12.58
40.00
1.00
26.46
1902.06
93.42
108.90
270.18
2.00
14.35
Figure 5.30 is a visual representation of the information given in Table 5.29
12
Pure Water
T = 25.00 C, P = 5.00 bar
Water + Solute
T = 63.00 C, P = 2.00 bar
Tray Absorber
T-302
11
Gas Mixture + Less Solute

T = 48.00 C, P = 1.00 bar
Gas Mixture + More Solute

T = 40.00 C, P = 1.00 bar
Figure 5.30 Visual representation of the inlet and outlet streams for tray absorption column T-302
141
5.8.3 Assumptions
In order to design the required tray absorption column, the following assumptions are made
Assume a single solute (acetic acid is available in negligible amounts)
Assume the operating pressure is that of entering stream number 9 (P = 1 bar)
Assume the operating temperature is that of the exit stream number 7 (T=63 C)
Assume the deviation factor D = 2.20
Assume the overall efficiency of the absorber is 60%
5.8.4 Equilibrium Line

Going back to the problem statement, one can see that both acrylic acid and acetic acid are
being absorbed. This indicates that both components are solutes. Compared to acrylic acid,
however, acetic acid is being absorbed in negligible amounts. As a result, the equilibrium line
calculations will be based on the thermodynamic data of acrylic acid only.
The relationship between the mole fraction in the vapor and liquid phases for absorption towers
can normally be represented in the form of a straight line known as Henrys Law
Y = HX
(5.47)
Where Y represents the mole fraction in the vapor phase, X the mole fraction in the liquid
phase, and H the slope of the line. The latter can be calculated as follows
H=D
p*
P
(5.48)
Where D is the deviation factor (normally ranges from 2.2 to 4) [49], p* the vapor pressure,
and P the total operating pressure. In our case, since the pressure varies along the column, the
operating pressure is assumed to take the value of the entering vapor stream. That is
P = 1.00 bar
142
As for the vapor pressure in equation (5.48), it can be calculated using the Antoine equation
B
p*i (mmHg) = 10 A - C + T
(5.49)
Where T is the temperature in C, and A, B, and C are component specific parameters. Table
5.30 gives the values of these parameters for acrylic acid. Note that the solute was assumed to
have the properties of pure acrylic acid.
Table 5.30 Constants A, B and C to be used with equation (5.49)
Species
Acrylic Acid
7.82557
1817.73000
226.60900
Proceeding in a similar manner, the operating temperature to be substituted into equation (5.49)
will be taken as equal to that of the exiting solvent stream
T = 63 C
Calculating the vapor pressure from equation (5.49)
1817.730
p*i = 10 7.82557 - 226.609 + 63 = 35.41 mmHg = 0.0472 bar

Note that the operating pressure is given in bars and therefore the vapor pressure was converted
using a suitable conversion factor. The deviation factor is obtained from literature [1]
D = 2.20
Calculating Henrys constant from equation (5.48)
H = 2.2
0.0472
= 0.1038
1
The equilibrium line from equation (5.47) is therefore

Y = 0.1038X
143
(5.50)
Equation (5.50) is a straight line for which only two points are needed to plot. Taking any two
arbitrary values for X, say 0 and 1, we get the following
(X, Y) = (0, 0)
(X, Y) = (1, 0.1038)
Plotting these two points gives us what is called an equilibrium line that relates the
compositions of the liquid and vapor phases (see Figure 5.31).
Equilibrium Line
0.012
0.010
0.008
0.006
0.004
0.002
0.000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Figure 5.31 Plot of equation (5.50)
5.8.5 Theory
5.8.5.1 Operating Line Derivation
The process flow diagram for a countercurrent stage process is shown in Figure 5.32. The inlet
L stream is Lo and the inlet V stream is VN+1 . The outlet product streams are V1 and LN and
the total number of stages is N. The component A is being exchanged between the V and L
streams. The V stream is composed mainly of component B and the L stream of component C.
Components B and C may or may not be somewhat miscible in each other. The two-phase
system can be gas-liquid, vapor-liquid, liquid-liquid, or other.
144
Figure 5.32 Countercurrent multiple-stage process.
Making a total overall balance on all stages,

L0 + VN+1 = LN + V1 = M
(5.51)
Where VN+1 is the mol/h entering, LN the mol/h leaving the process, and M the total flow. Note
that in Figure 5.32, any two streams leaving a stage are in equilibrium with each other. For
example, in stage n, Vn+1 and Ln , are in equilibrium. For an overall component balance on A,
B, or C,
L0 X0 + VN+1 YN+1 = LN XN + V1 Y1 = MXM
(5.52)
Where X and Y are mole fractions. Flows in kg/h (lbm/h) and mass fraction can also be used
in these equations. Making a total balance over the first n stages,
L0 + Vn+1 = Ln + V1
(5.53)
Making a component balance over the first n stages,

L0 X0 + Vn+1 Yn+1 = Ln Xn + V1 Y1
(5.54)
Solving for yn+1 in equation (5.54)

Yn+1 =
Ln Xn V1 Y1 - L0 X0
+
Vn+1
Vn+1
(5.55)
This is an important material balance equation, often called an operating tine. It relates the
concentration Yn+1 in the V stream with xn in the L stream passing it. The terms V1, Y1, L0 and
X0 are usually known or can be determined from equations (5.51) and (5.54).
145
5.8.5.2 Graphical Determination of the Theoretical Number of Stages

To determine the number of ideal stages required to bring about a given separation or reduction
of the concentration of acrylic acid and acetic acid from YN+1 to Y1 is often done graphically.
Starting at stage 1, Y1 and X0 are on the operating line. The vapor Y1 leaving is in equilibrium
with the leaving X1 and both compositions are on the equilibrium line. Then Y2 and X1 are on
the operating line and Y2 is in equilibrium with X2 and so on. Each stage is represented by a
step drawn in Figure 5.33. The steps are continued on the graph until YN+1 is reached.
Figure 5.33 - Number of stages in a countercurrent multiple-stage contact process
5.8.5.3 Analytical Determination of the Theoretical Number of Stages

When the flow rates V and L in a countercurrent process are essentially constant, the operatingline equation (5.55) becomes straight. If the equilibrium line is also a straight line over the
concentration range, simplified analytical expressions can be derived for the number of
equilibrium stages in a countercurrent stage process. Rearranging equation (5.52)
LN XN - VN+1 YN+1 = L0 X0 - V1 Y1
(5.56)
Rearranging equation (5.54) as well

L0 X0 - V1 Y1 = Ln Xn - Vn+1 Yn+1
146
(5.57)
Equating equation (5.56) to (5.57),

Ln Xn - Vn+1 Yn+1 = LN XN - VN+1 YN+1
(5.58)
Since the molar flows are constant, Ln = LN = constant = L and Vn+1 = VN+1 = constant = V.
Equation (5.58) then becomes
L(Xn - XN ) = V(Yn+1 - YN+1 )
(5.59)
Since Yn+1 and Xn+1 are in equilibrium, and the equilibrium line is straight, Yn+1 = mXn+1 .
Also, YN+1 = mXN+1 . Substituting mXn+1 for Yn+1 and calling A = L/mV , equation (5.59)
becomes
Xn+1 - AXn =
YN+1
- AXn
m
(5.60)
Where A is an absorption factor. All factors on the right-hand side of equation (5.60) are
constants. This equation is a linear first-order difference equation and can be solved by the
calculus of finite-difference methods. The final derived equations are as follows. For transfer
of solute A from phase V to L,
YN+1 - Y1
(A)N+1 - (A)
=
YN+1 - mX0
(A)N+1 - 1
(5.61)
Solving for N,
ln [
N=
YN+1 - mX0
1
1
(1 - ) + ]
Y1 - mX0
A
A
ln(A)
(5.62)
Where A is equal to
A = A1 AN
147
(5.63)
Where the values of A1 and AN are

L0
m1 V1
(5.64)
LN
mN VN+1
(5.65)
A1 =
AN =
5.8.6 Calculations
5.8.6.1 Graphical Determination of the Theoretical Number of Stages
The theoretical number of stages are now determined graphically in the manner described in
section 5.8.5.2. The results are plotted in Figure 5.34.
No. of Stages (Graphical Method)

0.012
0.010
0.008
0.006
0.004
0.002
0.000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
Figure 5.34 Graphical determination of the theoretical number of stages
From Figure 5.34, it can be seen that approximately 4.7 stages are required.
5.8.6.2 Analytical Determination of the Theoretical Number of Stages
From equation (5.64), A1 is equal to
A1 =
253.8
= 1.017
0.1038 2403.79
148
0.10
And AN from equation (5.65)

AN =
267.37
= 1.065
0.1038 2417.37
A is the geometric average between A1 and AN, as defined by equation (5.63)

A = 1.017 1.065 = 1.04
The number of stages can now be obtained analytically using equation (5.62)
0.00676
1
1
ln [0.00108 (1 - 1.04) + 1.04]
N=
= 4.7 stages
ln(1.04)
The number of stages must be an integer. By rounding off, we obtain 5 stages.
5.8.6.3 Actual Number of Stages
In the previous analysis, we have assumed that the vapor leaving each stage was in equilibrium
with the liquid leaving the same stage. This analysis assumed that stages are operating at 100%
efficiency. However, in actual practice, the stages are not perfect, i.e. there are deviations from
ideal conditions.
Therefore in actual operation the vapor and liquid streams leaving a stage are not in
equilibrium. We define the overall column efficiency EO as follows
EO =
No. of theoretical stage

No. of actual stage
(5.66)
The overall efficiency was assumed to be 60%. Rearranging equation (5.66) and solving for
the actual number of stages,
No. of actual stages =
5
= 8.33 9 stages
0.6
149
5.8.6.4 Minimum Solvent Flow and Maximum Discharge Concentration

After calculating the number of stages, it is desired to determine the maximum allowable
discharge concentration of the solvent along with its corresponding minimum flow. This is
evaluated by recalling the operating line equations (5.54) and (5.55). It is evident that the slope
of the operating line decreases with decreasing solvent flow until an ultimate condition is
approached. That is, when YN+1 and XN reach equilibrium. The maximum allowable
concentration is then measured as follows
XNmax = YN+1 /H = 0.00676/0.1038 = 0.0651
To get L'min, equation (5.54) is recalled with making Li and Vi equal to L'/(1 - Xi) and V'/(1 Yi), respectively, where L' and V' are the solvent and immiscible gas flow, respectively.
Substituting XNmax gives
L'min
X0
YN+1
XNmax
Y1
+ V'
= L'min
+ V'
1 - X0
1 - YN+1
1 - XNmax
1 - Y1
(5.67)
Substituting all known values into the equation
0 + (2401.02)
0.00676
0.0651
0.00108
= L'min
+ (2401.02)
1 - 0.00676
1 - 0.0651
1 - 0.00108
Solving for L'min

L'min = 197.50 kmol/h
The value of L'/L'min is obtained and compared with the optimum ratio range which lies between
1.2 and 1.5 [2]. L' is equal to L0 = 253.8. Thus,
L'/L'min = 253.8/197.5 = 1.285
Which indicates that the column operates within the optimum range. For more representative
explanation on operating at minimum liquid flow, Figure 5.35 shows the operating line at
maximum XN = 0.0651 and at L'min =197.50.
150
Operating Line at L'min

0.012
0.010
0.008
0.006
0.004
0.002
0.000
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
Figure 5.35 Operating line at minimum liquid flow
5.8.6.5 Column Height

In order to quantify the column height, the tray spacing must be first specified after determining
the actual number of trays within the column. Tray spacing can be determined as a cost
optimum, but is considerably set by mechanical factors. The most common tray spacing is 0.6
meters spacing which prevents flooding and facilitate the ease of maintenance whenever is
required.
From previous calculations, the actual number of trays = 9 and hence there are 8 spaces inbetween. Add to that top and bottom disengaging space and we obtain the following
Tower height = 8 spaces 0.6 m + 1.5 m (top) + 1.5 m (bottom) = 7.8 m
5.8.6.6 Column Diameter
The flooding condition fixes the upper limit of vapor velocity. A high vapor velocity is needed
for high plate efficiencies. The operating velocity is usually between 70 and 90% of that which
would cause flooding. For this design, a value of 80% of the flooding velocity will be used.
151
The flooding velocity can be estimated from the correlation given by Fair
-
uf = K1 L v
v
(5.68)
K1 is a constant obtained from Figure 5.36. The x-axis is defined by
FLV =
Lw
v
Vw L
(5.69)
Where Lw and Vw are the liquid and vapor molar flowrates, respectively.
Figure 5.36 Fair correlation for calculating the flooding velocity
It is shown in the material balance sheet that the fluid at the bottom of the column is more
concentrated and thus has a higher flowrate. Therefore, to ensure the column is able to
withstand the load, the diameter will be determined based on LN and VN+1 flowrates and
conditions (column bottom values). The total flow rate of the liquid flow exits the bottom of
the column is obtained previously and equal to
Lw = LN = 267.37 kmol/h
152
And the flow rate of gas enters the bottom of the column is also obtained and equal to:
Vw = VN+1 = 2417.37 kmol/h
To simplify calculations, the liquid at the bottom of the column is assumed to consist of water
only. Table 5.31 shows the physical properties of water at the temperature of 63.0 C
Table 5.31 Physical properties of water at 63.0 C
Property
Value
981.3520
18
0.0654
Equation (5.69) shows that the gas density is required to be calculated. Therefore, an average
molecular weight is obtained by applying the following
(5.70)
Mwtav = Yi Mwti
Where Yi is the vapor molar composition of stream 9 (N+1), and Mwt i is the molecular weight
of the ith component. Table 5.32 shows the tabulated calculation of Mwtav.
Table 5.32 average molecular weight calculation
Component
Mw (kg/kmol)
Mw Y (kg/kmol)
Propylene
42.000
0.011
0.460
N2
28.000
0.787
22.031
O2
32.000
0.039
1.237
CO2
44.000
0.045
1.982
H2O
18.000
0.112
2.012
Acetic Acid
60.000
0.001
0.050
Acrylic Acid
72.000
0.006
0.427
Average Molecular Weight
153
28.1986
Consequently, the average gas density is calculated by applying the ideal gas law as follows
v =
Mwtav P
RT
(5.71)
Where T is the temperature in Kelvin and P is the pressure in Pa. Both the temperature and
pressure are that of stream 9. Substituting into equation (5.71)
v =
28.1986 105
= 1.0836 kg/m3
8314 (40 + 273)
Next, we use equation (5.69) to calculate the factor FLV for conditions at the column bottom
FLV =
267.37
1.0836
= 0.004
2417.37 981.352
We use Figure 5.36 to obtain the value of K1. Note that the assumed tray spacing was 0.6 m. It
is shown that the minimum value of FLV is 0.01, which is greater than 0.004. As an
approximation, the value of K1 is taken as the minimum value of FLV. Then,
K1 = 0.100
The value of K1 applies to non-foaming systems and trays meeting certain hole and weir size
restrictions. It will need to be corrected for surface tension as follows
0.0654 0.2
K1 = 0.100 (
) = 0.127
0.0200
Using equation (5.68) to calculate the flooding velocity for bottom conditions
981.352 - 1.0836
uf = 0.127
= 3.812 m/s
1.0836
As mentioned previously, an operating velocity of 80% the flooding velocity is acceptable. So,
uf = 3.812 0.8 = 3.050 m/s
154
Calculating the gas volumetric flowrate at the bottom conditions:
v=
2417.37 28.1986
= 17.474 m3 /s
3600 1.0836
Calculating the net required area by dividing the volumetric flowrate by the corresponding
operating velocity
A=
17.474
= 5.73 m2
3.050
The downcomer area is usually 12% the total area. The column cross sectional area is therefore,
Cross-Sectional Area =
5.73
= 6.511 m2
0.88
Calculating the diameter for both conditions
4 6.511
D =
= 2.879 m
This is the diameter to be selected that prevents flooding from happening

5.8.6.7 Tray Selection
A sieve tray is selected due to its favorable price, ease of maintenance and common usage in
different applications. The tray material of construction is 18/8 stainless steel that has a higher
corrosion resistance (which is required, since the liquid-gas interaction occurs at its surface).
5.8.6.8 Material of Construction
In designing the column, it is favorable to use carbon steel as the construction material for the
larger parts of the column, such as the vessel, due to its attracting cost. Unfortunately, carbon
steel corrodes with acids. Therefore the vessel will be made from carbon steel and coated with
18/8 stainless steel from the inside (to prevent the parts that interact with acids from corroding).
155
5.8.7 Summary
Table 5.33 T-301 absorption column specifications
Liquid Feed Composition
X0 = 0.0000 (for solute)
Liquid Discharge Composition
XN = 0.05143 (for solute)
Gas Feed Composition
YN+1 = 0.00676 (for solute)
Gas Discharge Composition
Y1 = 0.00108 (for solute)
Operating Conditions
(T = 63.00 C, P = 1.00 bar)
Water Flow L'
kmol/h
253.80
Gas Flow V'
kmol/h
2401.02
L'min
kmol/h
197.50
XNmax
0.0651
Overall Efficiency
60%
Flooding Velocity
m/s
3.812
Operating Velocity
m/s
80% of flooding velocity

Number of Actual Trays
Tray Type
Sieve
Tray Spacing
0.6
Top/Bottom Space
Height
7.8
Diameter
2.879
Downcomer Area
m2
12% of the total cross sectional area
1.5
1.5
Column MOC
Carbon steel with 318 stainless steel coating
Trays MOC
318 stainless steel
156
Part Three
Reactor
157
5.9
Background of Reactors
5.9.1 General Description

Chemical reactions pertaining to the chemical, petrochemical and oil industries are performed
in special apparatus called reactors. There are distinct types of reactors intended to face
extremely varied operating conditions, both in terms of the nature of the chemical species
involved (reactants and products of the reaction) and of the physical conditions under which
they operate.
In general, a chemical reactor needs to be able to carry out at least three functions: provide the
necessary residence time for the reactants to complete the chemical reaction; allow the heat
exchange necessary; place the phases into intimate contact to facilitate the reaction [46].
To classify a reactor, the number of phases in the reactor itself, whether or not there are
agitation systems and the mode of operation (continuous reactor, semi-continuous or
discontinuous) need to be taken into consideration. It should also be noted that most chemical
reactors are equipped with heat exchange apparatus in the form of external jackets or internal
coils with a fluid flowing through them to act as a thermal vector to allow heat supply or
removal.
5.9.2 Batch and Continuous Flow

A variety of reactor designs are used in industry, but all of them can be assigned to certain basic
types or combinations of these. The basic combinations are: batch and continuous.
5.9.2.1 Batch Reactors
Batch reactors are used for most of the reactions carried out in a laboratory. The reactants are
placed in a test-tube, flask or beaker. They are mixed together, often heated for the reaction to
take place and are then cooled. The products are poured out and, if necessary, purified. This
procedure is also carried out in industry, the key difference being one of size of reactor and the
quantities of reactants [47]. Figure 5.37 shows an example of a batch reactor.
158
Figure 5.37 Diagram of a batch reactor
Batch reactors are usually used when a company wants to produce a range of products
involving different reactants and reactor conditions [47]. They can then use the same equipment
for these reactions.
5.9.2.2 Continuous Reactors
An alternative to a batch process is to feed the reactants continuously into the reactor at one
point, allow the reaction to take place and withdraw the products at another point. There must
be an equal flowrate of reactants and products. While continuous reactors are rarely used in the
laboratory, a water-softener can be regarded as an example of a continuous process (see Figure
5.38). Hard water from the mains is passed through a tube containing an ion-exchange resin.
Reaction occurs down the tube and soft water pours out at the exit.
Figure 5.38 Diagram of a continuous reactor
159
Continuous reactors are normally installed when large quantities of a chemical are being
produced. It is important that the reactor can operate for several months without a shutdown.
The product tends to be of a more consistent quality from a continuous reactor because the
reaction parameters (e.g. residence time, temperature and pressure) are better controlled than
in batch operations.
They also produce less waste and require much lower storage of both raw materials and
products resulting in a more efficient operation. Capital costs per ton of product produced are
consequently lower. The main disadvantage is their lack of flexibility as once the reactor has
been built it is only in rare cases that it can be used to perform a different chemical reaction.
5.9.3 Types of Continuous Reactors

Continuous flow reactors are used on an industrial level for large-scale plants and thus they
will be given special attention. The most common types of continuous reactors are: tubular,
fixed bed, and CSTR.
5.9.3.1 Tubular Reactor
In a tubular reactor, fluids (gases and/or liquids) flow through it at high velocities. As the
reactants flow, for example along a heated pipe, they are converted to products. At these high
velocities, the products are unable to diffuse back and there is little or no back mixing. The
conditions are referred to as plug flow. This reduces the occurrence of side reactions and
increases the yield of the desired product [47].
With a constant flowrate, the conditions at any one point remain constant with time and changes
in time of the reaction are measured in terms of the position along the length of the tube. The
reaction rate is faster at the pipe inlet because the concentration of reactants is at its highest and
the reaction rate reduces as the reactants flow through the pipe due to the decrease in
concentration of the reactant.
5.9.3.2 Fixed Bed Reactor
A heterogeneous catalyst is used frequently in industry where gases flow through a solid
catalyst (which is often in the form of small pellets to increase the surface area). It is often
described as a fixed bed of catalyst (see Figure 5.39).
160
Among the examples of their use are the manufacture of sulfuric acid (the Contact Process,
with vanadium (V) oxide as catalyst), the manufacture of nitric acid and the manufacture of
ammonia (the Haber process, with iron as the catalyst).
Figure 5.39 Diagram of a fixed bed reactor
5.9.3.3 Continuous Stirred Tank Reactor (CSTR)

In a CSTR, one or more reactants, for example in solution or as a slurry, are introduced into a
reactor equipped with an impeller (stirrer) and the products are removed continuously. The
impeller stirs the reagents vigorously to ensure good mixing so that there is a uniform
composition throughout. The composition at the outlet is the same as in the bulk in the reactor.
These are exactly the opposite conditions to those in a tubular flow reactor where there is
virtually no mixing of the reactants and the products.
161
Commented [HA6]:
5.10 Design of Reactor R-201

It is desired to design a reactor R-301 for the production process of acrylic acid. Three reactions
take place inside the reactor, producing the following products: acrylic acid, acetic acid, carbon
dioxide, and water. The reactants for the three reactions are propylene and oxygen. The
conversion of propylene is about 88.4 percent. The reactants enter the reactor at a temperature
of 191 C and the products exit at 310 C. Molten salt is used as a cooling medium to remove
excess energy from the reactor and enter countercurrent at a temperature of 200 C and exit at
250 C.
5.10.2 Flowrate of Inlet and Outlet Streams

The molar flowrate of the reactor inlet and outlet streams as well as temperatures and pressures
are given in Table 5.34.
Table 5.34 Reactor R-301 flowrates
Properties
Flowrate (kmol/h)
Stream
T (C)
P (bar)
C3H6
N2
O2
CO2
H2O
Acetic
Acrylic
191.00
4.30
228.60
1902.06
505.62
0.00
1831.68
0.00
0.00
310.00
3.50
26.46
1902.06
93.42
108.90
2098.62
11.77
158.02
Figure 5.40 is a visual representation of the information given in Table 5.34
4
Propylene = 228.60 kmol/h
N2 = 1902.06 kmol/h
O2 = 505.62 kmol/h
H2O = 1831.68 kmol/h
T = 191.00 C, P = 4.30 bar
Reactor
R-301
Propylene = 26.46 kmol/h

N2 = 1902.06 kmol/h
O2 = 93.42 kmol/h
CO2 = 108.90 kmol/h
H2O = 2098.62 kmol/h
Acetic = 11.77 kmol/h
Acrylic = 158.02 kmol/h
Coolant In
Coolant Out
Molten Salt
T = 250.00
Molten Salt
T = 200.00 C
Figure 5.40 Visual representation of the inlet and outlet streams for reactor R-301
162
5.10.3 Assumptions
In order to design the required reactor, the following assumptions are made
Steady state operation (neglect accumulation term)
Pseudo-homogeneous system (neglect catalyst deactivation)
Neglect pressure drop effects
5.10.4 Theory
Consider the following schematic diagram of the reactor:
FS
R-301
FS
Figure 5.41 Tubular reactor
By taking a differential element V of the reactor, the generalized mole balance equation, on
species S over the catalyst weight results in the following equation
FS|W - FS|(W+W) + rS V = 0
(5.72)
Note that for a steady state operation the accumulation term is neglected. Dividing both sides
by V and taking the limit as V 0 yields the following
dFS
= rS
dV
(5.73)
For the case of multiple reactions, equation (5.73) is applied on all the species involved in the
reactions. The rate rS is based on volume of reactor, and in our case, can be defined by the
power law. All component rate laws must be related back to the base rate law. To do so,
consider the following reaction
aA + bB cC + dD
163
The rate laws are related by the following formula

-rA -rB rC rD
=
=
=
a
b
c
d
(5.74)
In our case, all rate laws will be related back to propylene. If we substitute in equation (5.73)
for the reactant A, we get the following
dFA
= rA = -kA PA PB
dV
(5.75)
Where and are reaction based. Remember that we assumed the rate law applies here. The
reaction constant kA is defined by the Arrhenius equation as follows
-E
kA = AeRT
(5.76)
Thus it is a function of temperature. The differential equation (5.75) can be solved analytically
if the following conditions are met:
i.
The concentrations PA and PB can be expressed in terms of FA
ii.
The temperature in the reaction constant can be expressed in terms of F A
This indicates that the differential equation is a function of partial pressure as well as
temperature. The differential equation should also be a function of total pressure (since the
pressure dropped from 4.5 to 3.5 bar), but in our case, pressure drop effects have been neglected
to simplify calculations. The partial pressure PS can be related to FS as follows
PS =
FS
P0
FT
(5.77)
Where FT is the total molar flowrate for the outlet stream. It is defined by the following
FT = FA + FB + FC + FD + FInert
(5.78)
Note that equation (5.77) is valid when pressure drop effects are neglected. If not, then P0 (the
inlet pressure) is substituted with P (the pressure at any point down the length of the reactor).
164
5.10.5 Reaction Kinetics

In addition to the acrylic acid formation reaction, two additional by-reactions are taking place
C3H6 + 1.5O2 C3H4O2 + H2O
(R1)
C3H6 + 2.5O2 C2H4O2 + CO2 + H2O
(R2)
C3H6 + 4.5O2 3CO2 + 3H2O
(R3)
The reaction rate laws are given by the following [1]
-ri = ko,i exp [
-Ei
]P
P
RT Propylene Oxygen
(5.79)
Partial pressures are in kPa and the activation energies and pre-exponential terms for reactions
R1-R3 are given in Table 5.35.
Table 5.35 Kinetics of reactions R1-R3 [1]
i
Ei (kcal/kmol)
ko,i (kmol/m3 reactor/h/kPa2)
15,000
1.59 105
20,000
8.83 105
25,000
1.81 108
The kinetics presented above are valid in the temperature range, 250 370 C. Above 370 C
the catalyst starts to coke-up (carbon deposits on the surface of the catalysts causing it to
deactivate), and below 250 C the rate of reaction drops off rapidly [1]. Due to these effects,
the catalysts should never be operated outside of these temperature limits.
5.10.6 Thermodynamic Properties

Prior to proceeding to design calculations, it is necessary to determine the thermodynamic
properties for all the components involved in the reaction. These properties are the heats of
formation and the vapor heat capacities. Both properties are temperature-dependent and thus
have to be obtained in terms of temperature.
165
The specific heat capacity can be correlated as a function of temperature using the following
polynomial form
Cp = Ai + Bi T + Ci T2 + Di T3
(5.80)
Where Ai , Bi , Ci and Di are component-dependent coefficients and are given in Table 3, and T
is the temperature in K. Note that equation (5.80) gives the heat capacity Cp in the units of
kJ/kmol/K.
Table 5.36 Heat capacity coefficients to be used with equation (5.80) [2]
Comp
C3H6
N2
O2
CO2
H 2O
Acetic
Acrylic
31.298
28.986
31.320
27.437
30.092
34.85
7.755
B 103
72.450
1.854
-20.235
42.320
6.832
37.630
293.860
C 106
194.810
-9.647
57.866
-19.555
6.793
283.110
-208.78
D 109
-215.800
16.635
-36.506
3.997
-2.534
-307.700
71.590
The heat of formation can be correlated as a function of temperature using the following
polynomial form
Hf i = i + i T + i T2
(5.81)
Where i , i and i are component-dependent coefficients and are given in Table 5.37, and T
is the temperature in K. Note that equation (5.81) gives the heat of formation Hf i in the units
of kJ/kmol. Only those components involved in the reactions are considered, and oxygen is
neglected since its heat of formation is essentially zero.
Table 5.37 Heat of formation coefficients to be used with equation (5.81) [2]
Comp
C3H6
CO2
H 2O
Acetic
Acrylic
36342
-393880
-238410
-417910
-313180
-64.910
1.910
-12.256
-58.243
-40.894
C 103
30.500
2.110
2.770
33.500
21.000
166
The cooling medium properties are also needed. These are summarized in Table 5.38.
Table 5.38 Cooling medium physical properties [1]
Property
Value
Density (kg/m3)
2000
1.560
0.606
5.10.7 Design Calculations

5.10.7.1 Net Rate Laws
The mole balance equation (5.73) is applied for all the species involved in the reactions
dFPy
= rPy
dV
dFO2
= rO2
dV
dFAcrylic
= rAcrylic
dV
dFAcetic
= rAcetic
dV
dFCO2
= rCO2
dV
dFH2 O
= rH2 O
dV
Since nitrogen was not involved in any reaction, its corresponding rate is equal to zero. As
mentioned previously, since multiple reactions are occurring, all rate laws will be related to
propylene, but first, equation (5.74) must be written for both reactions. For the first reaction,
-rPy -rO2 rAcrylic rH2O
=
=
=
1
1.5
1
1
167
For the second reaction,

-rPy -rO2 rAcetic rCO2 rH2 O
=
=
=
=
1
2.5
1
1
1
And for the third reaction,
-rPy -rO2 rCO2 rH2 O
=
=
=
1
4.5
3
3
By expressing the net rate laws in terms of propylene, we obtain the following
rPy = r1Py + r2Py + r3Py
rO2 = r1O2 + r2O2 + r3O2 = 1.5r1Py + 2.5r2Py + 4.5r3Py
rAcrylic = r1Acrylic = -r1Py
rAcetic = r2Acetic = -r2Py
rCO2 = r2CO2 + r3CO2 = -r2Py - 3r3Py
rH2O = r1H2O + r2H2O + r3H2O = -r1Py - r2Py - 3r3Py
Where r1Py , r2Py and r3Py are defined by equation (5.79)
5.10.7.2 Heat of Reactions
The heat of reactions are a function of the heat of formation (and thus a function of
temperature). They can be evaluated by the following equation
n
HRxn j = vij Hf i
(5.82)
i=1
Where HRxn j is the heat of reaction j in kJ/kmol and n is the number of components involved.
168
By applying equation (5.82) to the three reactions involved in the process, we obtain the
following
HRxn 1 = (-1)Hf Py + (-1.5)Hf O + (1)Hf Acrylic + (1)Hf H
2
2O
HRxn 2 = (-1)Hf Py + (-2.5)Hf O2 + (1)Hf Acetic + (1)Hf CO2 + (1)Hf H2O

HRxn 3 = (-1)Hf Py + (-4.5)Hf O + (3)Hf CO + (3)Hf H
2
2O
Remember that the heats of formation are evaluated from equation (5.81) and Table 5.37. We
have successfully obtained the heat of reactions as a function of temperature.
5.10.7.3 Energy Balance on Process Stream
Since the reactor operates non-isothermally, the flowrate at any point along the length of the
reactor will depend upon the temperature. To account for temperature changes, the energy
conservation law must be applied on a differential element of the reactor. By applying the
general law on a differential element V, we obtain the following
3
FT Cp
mix
T|V + rj V (-HRxn j ) = FT Cp
j=1
mix
T|V+V + QR
(5.83)
Where CPmix is the specific heat capacity of the mixture and QR is the heat removed from the
reactor, as defined by the following
QR = UA(T Ta) = UaV(T Ta)
(5.84)
Where U is the overall heat transfer coefficient in kJ/h, Ua the overall heat transfer coefficient
for unit area per volume of reactor, A the heat exchanger area, and Ta the temperature of the
cooling medium. Substituting equation (5.84) into (5.83) and dividing both sides by V and
taking the limit as V 0 yields the following
3
dT j=1 rj (-HRxn j ) - Ua(T Ta)
=
dV
FT Cp
mix
169
(5.85)
Expanding the summation term yields the following

dT [r1Py (-HRxn 1 ) + r2Py (-HRxn 2 ) + r3Py (-HRxn 3 )] - [Ua(T - Ta )]
=
dV
FT Cp
(5.86)
mix
The negative sign is convention for an exothermic reaction.

5.10.7.4 Energy Balance on Cooling Medium
Since equation (5.86) is a function of yet another variable parameter, the cold fluid temperature
Ta , the general heat balance equation must be applied on the cooling medium in a similar
manner to that given in equation (5.83). The differential analysis yields the following
Fc Cp Ta |V+V + UaV(T Ta) = Fc Cp Ta |V
c
(5.87)
Dividing both sides of equation (5.87) by V and taking the limit as V 0 yields
dTa Ua(T Ta)
=
dV
mc Cp
(5.88)
5.10.7.5 Algebraic Equations

We can see from equation (5.79) that the rate laws are functions of the partial pressures of
propylene and oxygen, which in turn are functions of temperature. Since the reactor is not
isothermal, the partial pressure values vary down the length of the reactor. The partial pressures
must therefore be expressed in terms of temperature. To do so, the ideal gas law is used, which
cancels out to become in the form of equation (5.77). Applying equation (5.77) on oxygen and
propylene yields the following
PPy =
FPy
P0
FT
(5.89)
PO 2 =
FO 2
P0
FT
(5.90)
Note that we have used the inlet pressure P0 instead of the pressure at any point down the length
of the reactor P because we have neglected pressure drop effects.
170
In addition to defining the partial pressures in terms of temperature, the following algebraic
equations have to be inserted into Polymaths ODE solver
P0 = 430
(5.91)
Ua = 277533.5
(5.92)
mc = 1926000
(5.93)
Cpc = 1.56
(5.94)
The algebraic equations (5.91) through (5.94) must be inserted into Polymath using computer
syntax, i.e. P0 is inserted as P0 and Ua is inserted as Ua.
5.10.7.6 Differential Equations Initial Values
Eight differential equations are involved in the calculations, and hence eight initial values must
be set. Below is a summary the eight differential equations along with the initial conditions.
Differential Equation
Type
Initial
dFPy
= rPy
dV
Mass
228.60
dFO2
= rO2
dV
Mass
505.62
dFAcrylic
= rAcrylic
dV
Mass
0.00
dFAcetic
= rAcetic
dV
Mass
0.00
dFCO2
= rCO2
dV
Mass
0.00
dFH2 O
= rH2 O
dV
Mass
1831.68
dT [r1Py (-HRxn 1 ) + r2Py (-HRxn 2 ) + r3Py (-HRxn 3 )] - [Ua(T - Ta )]

=
dV
FT Cp
Energy
464.15
dTa Ua(T Ta)

=
dV
mc Cp
Energy
473.15
mix
171
5.10.7.7 Solving Using Polymaths ODE Solver

The differential equations presented in section 5.10.7.6, along with the net rate laws discussed
in section 5.10.7.1, the heat of reactions discussed in section 5.10.7.2, the algebraic equations
discussed in section 5.10.7.5, and the physical data (heats of capacity, heats of formation, etc.),
are written into Polymaths ODE solver. A summarized (short) output of the software is shown
in Table 5.39 and Figure 5.42. For complete input and output of Polymath, please refer to
Appendix 3.
Table 5.39 Polymaths ODE solver output
Variable
Initial Value
Minimum Value
Maximum Value
Final Value
Volume (m )
0.00
0.00
2.56
2.56
FPy (kmol/h)
228.60
26.51
228.60
26.51
FO2 (kmol/h)
505.62
94.24
505.62
94.24
FAcrylic (kmol/h)
0.00
0.00
158.19
158.19
FAcetic (kmol/h)
0.00
0.00
11.74
11.74
FCO2 (kmol/h)
0.00
0.00
108.24
108.24
FH2 O (kmol/h)
1831.68
1831.68
2098.10
2098.10
FN2 (kmol/h)
1902.06
1902.06
1902.06
1902.06
T (K)
464.15
464.15
860.41
588.15
Ta (K)
473.15
473.15
522.80
522.80
5.10.7.8 Reactor Dimensions

From Table 5.39, we see that a reactor volume of 2.56 m3 gives the required conversion of
propylene. What is left is the determination of the reactor diameter. Many references cite the
optimum reactor diameter as one third its length [3], or in other words
D = 1/3L
(5.94)
For a cylindrical reactor, the volume is given by

V=
2
D L
4
172
(5.95)
C ha p te r Fi ve : E qui pme n t D es i gn
Figure 5.42 Polymaths ODE solver output
173
Substituting equation (5.94) into (5.95) yields the following

V=
(1/3L)2 L
4
(5.96)
Substituting V = 2.56 m3 into equation (5.96) and solving for the reactor length L gives the
following
L = 3.084 m
And the corresponding diameter from equation (5.94)
D = 1/3(3.084) = 1.028 m
5.10.7.9 Reactor Catalyst
In order to calculate the amount of catalyst needed to effect such a conversion of propylene, its
physical properties are needed. These are summarized in Table 5.40.
Table 5.40 Catalyst physical properties [1]
Property
Value
Particle Diameter dp (mm)

Catalyst Density Cat
(kg/m3)
2100
Porosity
0.45
The mass of catalyst can be calculated by using the following

W = Vcat (1 - )
Substituting into equation (5.97),
W = 2.56 2100(1 - 0.45) = 2956.8 kg
174
(5.97)
5.10.7.10 Conversion of Propylene

The calculation of conversion is based in the limiting reactant, propylene. Its value is given by
equation (5.98)
X=1-
FPy
(5.98)
F0Py
By substituting the initial and final values of the flowrate of propylene from Table 5.39, we
obtain the following
X=1-
26.46
= 0.884 = 88.42%
228.60
5.10.7.11 Yield
The yield is calculated from equation (5.99) based on the amount of limiting reactant reacting
to form the main product. In other words, how much propylene will react to form acrylic acid.
Y=
FAcrylic - F0Acrylic
(5.99)
F0Py
Substituting the initial and final amount of acrylic acid from Table 5.39 gives the following
Y=
158.02 - 0
= 0.691 = 69.1%
228.60
5.10.7.12 Selectivity
The selectivity is calculated as the amount of main product formed to the amount of side
product. In other words, the amount of acrylic acid to the amount of acetic acid, and also the
amount of acrylic acid to the amount of carbon dioxide.
Selectivity (AA/Acetic Acid) =
Selectivity (AA/CO2 ) =
175
158.02
= 13.425
11.77
158.02
= 1.451
108.90
5.10.7.13 Space time

Space time is defined as the time necessary to process one reactor volume of fluid based on
entrance conditions (holding time or mean residence time). It is obtained by dividing the reactor
volume by the volumetric flowrate entering the reactor, as given by equation (5.100)
V
v0
(5.100)
The volumetric flowrate entering the reactor v0 is calculated from the ideal gas law
v0 =
FT0 RT0
P0
(5.101)
Where FT0 is given by a form similar to that of equation (5.78)

FT0 = 228.60 + 505.62 + 1831.68 + 1902.06 = 4467.96 kmol/h
Substituting into equation (5.101) to solve for the entering volumetric flowrate
v0 =
4467.96 8.314 464.15

= 40096.75 m3 /h
430
Hence the space time from equation (5.100) is
2.56
= 6.38 10-5 hours = 0.23 seconds
40096.75
5.10.7.14 Material of Construction

The best material for construction of the reactor is high alloy stainless steel. Cast iron is not
particularly strong or tough and is therefore not able to sustain the high reactor temperatures.
Several other alloys, such as nickel-based alloys, could be used, but would not be the most
economical option [4]. Due to these conclusions, high alloy stainless steel would be the best
option, as it offers a balance between its ability to sustain high temperatures and its price.
176
5.10.8 Summary
Table 5.41 R-301 reactor specifications
Fluid Allocation
Cooling Jacket (MSalt)
Reactor (HC mixture)
Process Flowrate (In/Out)
kmol/h
4467.96
4399.25
Coolant Flowrate (In/Out)
kg/h
1926000
1926000
Inlet Temperature
200 (Coolant)
191 (Process stream)
Outlet Temperature
250 (Coolant)
310 (Process stream)
Inlet Pressure
bar
4.3 (Process stream)
Outlet Pressure
bar
3.5 (Process stream)
kJ/m /h/K
277533.5
Diameter
1.028
Length (z)
3.084
Volume
m3
2.56
Ua
Conversion of Propylene
88.41%
Yield Y
69.1%
Selectivity (AA/Acetic Acid)
13.425
Selectivity (AA/CO2)
1.451
Reactor Type
Fixed bed reactor
High alloy stainless steel

Catalyst Specifications
Shape
Spherical
Type
Molybdenum and vanadium alloy

0.45
Void fraction ()
DP
Density (c )
Weight
mm
kg/m3
2100
kg
2956.8
177
178
Chap te r Six: P rocess Co ntro l a nd Ins trumen ta tio n
CHAPTER SIX
Process Control and Instrumentation
6.1
Introduction
6.1.1 Definition
Control is used to modify the behavior of a system so that it behaves in a specific desirable way
over time. Control is an interconnection of components forming a system configuration that
will provide a desired system response. The controlled process has an input and output
variables, as shown in Figure 6.1. Its response is described in terms of dependence of the output
variable on the input variable.
Variables such as pressure, temperature or flowrate usually have to be set on significant
conditions. This setting should not change while the process is running. The controlled variable
is first measured and an electrical signal is created to allow an independent control loop to
control the variable. The measured value in the controller must then be compared with the set
point value desired. The result from the comparison determines any action that needs to be
taken. At the end, a suitable location has to be determined in the system where the controlled
variable can be influenced.
Input
Output
Process
Figure 6.1 Diagram shown the input and output of a process
179
6.1.2 Control Terminology

Table 6.1 contains the terminology most often associated with control systems
Table 6.1 Control terminology
Term
Definition
The variables which quantify the performance or quality of the final

Controlled variable
product. They are also called output variables.
These input variables are adjusted dynamically to keep the controlled

Manipulated variable
variables at their set-points.
These are also called load variables and represent input variables that
Disturbance
can cause the controlled variables to deviate from their respective set
points.
Set by the operator, master controller or computer as a desired value for a

Set point
controlled variable. It is also called sometimes as reference value.
The set-point signal is changed and the manipulated variable is adjusted

Set point change
appropriately to achieve the new operating conditions. Also called

servomechanism (or servo) control.
The process transient behavior when a disturbance enters, also called
Disturbance change
regulatory control or load change. A control system should be able to

return each controlled variable back to its set-point.
180
6.1.3 Process Control Objectives

The primary objectives of the designer when specifying instrumentation and control schemes
are as follows:
Safety
The safe operation of chemical process is a primary requirement for the well-being of the
people in the plant and for its continued contribution to the economic development. The
operating pressures, temperatures, and concentration of chemicals should always be within the
allowable limits [1].
Product specifications
A plant should produce the desired amounts and quality of the final product. The objective here
is to produce 89211.35 ton/year of acrylic acid with 99.94 mole% purity. In achieving this, a
control system is needed to ensure that the production level and the purity are satisfied.
Environmental regulations
Various laws may specify that the temperatures and concentrations of the effluents from a
chemical plant be within certain limits. Therefore, the process of manufacturing acrylic acid
must conform to Saudi Arabias environmental laws and regulations.
Operational constraints
The various types of equipment used in a chemical plant have constraints inherent to their
operations. Such constraints should be satisfied throughout the operation of the plant. It is very
important to ensure that the pumps always maintain a certain net positive suction to avoid
cavitations, tanks should not overflow or go dry, distillation columns should not be flooded,
the temperature in catalytic reactor should not exceed an upper limit to avoid catalyst sintering,
etc. Control systems are needed to satisfy all these operational constraints.
Economics
The operation of the plant must conform to the market condition, that is, the availability of
raw materials and the demand of the final products. Furthermore, it should be as economical
as possible in its utilization of raw materials, energy, capital, and human labor. Thus, it is
required that the operating conditions are controlled at given optimum levels of minimum
operating cost, maximum profit, and so on.
181
All the requirements listed previously 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 operator), which together constitute the control system. There are three
general classes of needs that a control system is called on to satisfy [2]:
Suppressing the influence of external disturbances
Ensuring the stability of a chemical process
Optimizing the performance of a chemical process
6.1.4 Types of Control Systems

Some of the most widely used control configurations are: feedforward, feedback, ratio, and
cascade control systems. Further descriptions of these configurations are given below.
Feedforward control system
Feedforward control is based on measuring the change in a process unit, anticipating the effect
that the change will have on the process and automatically taking corrective action on another
input variable to counteract the change. It is usually specified where changes in process inputs
occur so frequently that the feedback controller cannot keep up or if the disturbances are so
large that the controlled variable cannot be kept within tolerable limits.
Feedback control system
Feedback is designed to achieve and maintain the desired process output conditions by
measuring the output variable and checking its value against a set point, then modifying the
controlled input variable to reach this set point. Feedback control is more successful in reaching
the target set point than feedforward control but it responds more slowly since it reacts only to
an output upset that is detected only a certain length of time after a process input has changed
and caused the upset.
182
Rate control system
In certain processes, it is often necessary to maintain the relative proportions of two variables
constant by ratio control. Ratio control is a special type of feedforward control that has been
widely used in the process industries. The main purpose is to maintain the ratio of two variables
at a specified value. The actual ratio of the two process variables is controlled rather than
controlling the individual variables.
Cascade control system
Cascade control design considers the likely disturbances and tailors the control system to the
disturbance(s) that strongly degrades performance. The control uses an additional, secondary
measured process input variable that has the important characteristic that it indicates the
occurrence of the key disturbance. In other words, a cascade control strategy combines two
feedback controllers, with the primary controller's output serving as the secondary controller's
set point.
6.2
Acrylic Acid Plant Control Systems
6.2.1 R-301: Reactor

The control objectives of the reactor are: to maintain the non-isothermal profile of the reactor
in order to prevent runaway reaction, to maintain the same feed flow into the process, and to
maintain the overall safety of the process by adding extra devices such as the pressure relief
valve (PSV). Table 6.2 and Figure 6.2 show the control strategy and the arrangement for the
reactor R-301.
Table 6.2 Control Strategy for Reactor, R-301
Controlled
Variable
Measured
Variable
Manipulated
Variable
Controller Type
Set Point
Reactor inlet feed

flow
Reactor inlet feed

flow
Inlet flowrate
Feedback control
FC 04
F = 4467.96
kmol/h
Reactor
temperature
Reactor
temperature
Molten salt inlet

flowrate into
reactor
Cascade control
TC 01
N/A
Reactor operating
pressure
Reactor operating
pressure
Reactor outlet
flowrate
Cascade control
PC 01
P = 4.3 bar
183
Figure 6.2 Control system for reactor R-301
6.2.2 T-303: Distillation Column

Distillation column T-303 is used to separate a mixture that has a composition of 6.48 mol%
acetic acid and the balance is acrylic acid. Acetic acid is to be separated in the distillate with a
purity of 99.82 mol%. The bottom product stream should contain maximum 0.06 mol%. The
control system for this column aims at maintaining the pressure, temperature, flowrate, reflux
ratio, and level at safe conditions. Table 6.3 shows the control strategy for the distillation
column T-303.
Table 6.3 Control strategy for distillation column T-303
Controlled
Variable
Measured
Variable
Manipulated
Variable
Controller Type
Set Point
Column pressure
Pressure at top
tray
Flowrate of
Stream 17
Feedback
controller PC 04
P = 0.19 bar
Column top
temperature
Temperature at
top tray
Cooling water
flowrate in
condenser
Cascade
controller TC 02
FC 09
T = 47 0C
184
Liquid level at
the bottom
Liquid level at
bottom tray
Flowrate of
stream 18
Feedback
controller
LC 03
Liquid level
Optimum reflux
ratio
Reflux and
distillate flowrate
Distillate stream
Ratio controller
RC 01
R = 30.5
Column bottom
temperature
Temperature at
bottom tray
Flowrate of
steam
Cascade
controller TC 3
FC 11
T = 89 C
Inlet flowrate to
the column
Inlet flowrate
Inlet flowrate
Feedback
controller
FC 10
F = 167.74
kmol/h
The flowrate of both the distillate at stream 17 and the reflux stream are measured by the flow
transmitter (FT). The flow signals are then sent to the divider function block and the output
will be sent to the ratio controller (RC). Any deviation signals from the divider function block
will then actuate the control valve to adjust the flow of the reflux stream accordingly. Figure
6.3 shows the arrangement of the controls used for T-303 unit.
Figure 6.3 Control system for distillation column T-303
185
Due to the slow dynamic response of a column system, a cascade control with a primary loop
of temperature controller and secondary loop of flow controller is implemented. The cascade
control is placed to improve the dynamic response of the system and also to eliminate possible
disturbances that may be caused by fluctuation of flowrate of steam. Since the dynamic
response of the secondary loop is faster than the primary loop, the flow controller should be
able to adjust the flow steam to the reboiler based on the set point of the temperature controller.
The signal detected by level transmitter (LT) is sent to the level controller (LC) for further
control of the valve opening to equal the level to the set point.
6.2.3 T-302: Absorber Tower

Absorption tower, T-302 is used to absorb acetic acid and acrylic acid from a mixture of
propylene, oxygen, nitrogen, carbon dioxide, water, acetic acid, and acrylic acid. The vapor
stream fed to the tower contains 2.00 and 14.35 kmol/h of acetic acid and acrylic acid,
respectively, and an amount equal to 1.17 and 12.58 kmol/h, respectively, is to be recovered.
Pure water (solvent) enters the tower at 25.00 C and 5.00 bar. The control system for this
column aims at maintaining the pressure, flowrate, and level at safe conditions. Table 6.4 shows
the control strategy for the absorber T-302.
Table 6.4 Control strategy for Absorber T-302
Controlled
Variable
Measured
Variable
Manipulated
Variable
Controller Type
Set Point
Tower pressure
Pressure at top
tray
Flowrate of
Stream 11
Feedback
controller PC 03
P = 1 bar
Liquid level at
the bottom
Liquid level at
bottom tray
Flowrate of
stream 7
Feedback
controller
LC 02
Liquid level
Water inlet
flowrate to the
absorber
Water inlet
flowrate to the
absorber
Water inlet
flowrate to the
absorber
Feedback
controller
FC 07
F = 253.8 kmol/h
186
6.2.4 Heat Exchangers

In this category, there two coolers (E-302) and (E-305). Temperature control of E-302 is one
of the most important parameter that needs attention. A higher the temperature outlet from heat
exchanger E-302 will reduce the separation in extraction unit, X-301. Therefore, the cooling
agent of this heat exchanger has to be controlled well in order to avoid any problems in other
units.
Table 6.5 shows the control strategy and the arrangement for the mentioned heat exchangers.
Table 6.5 Control strategy for E-302 and E-305
Unit
Measured
Variable
Controlled
Variable
Manipulated
Variable
Controller
Type
Set Point
E-302
Temperature
of the feed
Temperature
at stream 10
Inlet cooling
water flowrate
Feedback
control
FC08
T = 40C
E-305
Temperature
of the feed
Temperature
at stream 18
Inlet cooling
water flowrate
Feedback
control
FC12
T = 40 C
Figure 6.4 shows a summary of the flowsheet with all the control loops.
187
Chapter Six: Process Control and Instrumentation
Figure 6.4 Process flowsheet showing all control loops
188
Cos t a nd P r o fi ta b i l i t y Ana l ys is
CHAPTER SEVEN
Cost and Profitability Analysis
Part One: Capital Cost

7.1
Introduction
7.2
Estimation of Purchased Equipment Cost
7.3
Effect of Time on Purchased Equipment Cost
7.4
Bare Module Cost of Equipment at Base Conditions
7.5
Bare Module Cost of Equipment at Operating Conditions
7.6
Grassroots Cost
7.7
Calculations
Part Two: Manufacturing Costs

7.8
Introduction
7.9
Operating Labor Costs
7.10
Utility Streams Costs
7.11
Raw Materials Costs
7.12
Manufacturing Costs Calculations
Part Three: Profitability Analysis

7.13
Selling Price
7.14
Project Life
7.15
Cash Flow and Interest Rate
7.16
Taxation and Depreciation
7.17
Cash Flow Diagram for a New Project
7.18
Profitability Criteria for Project Evaluation
7.19 Analysis and Calculations
189
Part One
Capital Cost
190
7.1
Introduction
Capital costs are fixed, one-time expenses incurred on the purchase of land, buildings,
construction, and equipment used in the production of goods or in the rendering of services.
Put simply, it is the total cost needed to bring a project to a commercially operable status.
Whether a particular cost is capital or not depend on many factors such as accounting, tax laws,
and materiality.
Capital costs include expenses for tangible goods such as the purchase of plants and machinery,
as well as expenses for intangibles assets such as trademarks and software development.
Capital costs are not limited to the initial construction of a factory or other business. Namely,
the purchase of a new machine to increase production and last for years is a capital cost. Capital
costs do not include labor costs.
Unlike operating costs, capital costs are one-time expenses but payment may be spread out
over many years in financial reports and tax returns. Capital costs are fixed and are therefore
independent of the level of output.
For example, a fossil fuel power plant's capital costs include the following:
Purchase of the land upon which the plant is built
Permits and legal costs
Equipment needed to run the plant
Costs involving the construction of the plant
Financing and commissioning the plant (prior to commercial operation)
They do not include the cost of the natural gas, fuel oil or coal used once the plant enters
commercial operation or any taxes on the electricity that is produced. They also do not include
the labor used to run the plant or the labor and supplies needed for maintenance.
191
7.2
Estimation of Purchased Equipment Cost
To obtain an estimate of the capital cost of a chemical plant, the costs associated with major
plant equipment must be known. For the calculations presented here, the acrylic acid process
flowsheet (see Attachments) will be used as a basis. The equipment calculations will also be
based on the materials of construction and the size/capacity identified in design calculations.
The most accurate estimate of the purchased cost of a piece of major equipment is provided by
a current price quote from a suitable vendor. The next best alternative is to use cost data on
previously purchased equipment of the same type. Another technique utilizes summary graphs
or correlations available for various types of common equipment. The calculations presented
in this chapter will be presented on this last technique. Any cost data must be adjusted for any
difference in unit capacity and also for any elapsed time since the cost data were generated.
All the data for the purchased cost of equipment of this chapter were obtained from Turtons
Analysis, Synthesis and Design of Chemical Processes [44]. The data are obtained from a
survey during the period May to September of 2001, so the costs must be corrected for inflation.
Data for the purchased cost of the equipment, at ambient operating pressure (1 atm) and using
carbon steel construction, were fitted to the following equation:
log10 C0p (2001) = K1 + K2 log10 (A) + K3 [log10 (A)]
(7.1)
Where A is the capacity or size parameter for the equipment. The data for K1, K2, and K3, along
with the maximum and minimum values used in the correlation, are given in Table 7.1.
Table 7.1 Purchased equipment cost at base conditions [44]
Equipment
Description
K1
K2
K3
Furnace
Nonreactive
7.3488
-1.1666
0.2028
kW
Heat Exchanger
Floating head
4.8306
-0.8509
0.3187
m2
Vertical Vessel
Distillation/absorber
3.4974
0.4485
0.1074
m3
Vertical Reactor
Packed bed
3.4974
0.4485
0.1074
m3
Tray
Sieve
2.9949
0.4485
0.1074
m2
Pump
Centrifugal
3.3892
0.0536
0.1538
kW
Vaporizer
Thermosyphon
4.8306
-0.8509
0.3187
m2
192
7.3
Effect of Time on Purchased Equipment Cost
As mentioned previously, the data presented in Table 7.1 give the purchased equipment cost in
the year 2001. Therefore, it is essential to update these costs to take changing economic
conditions (inflation) into account. This can be achieved by using the following expression:
I2
C2 = C1 ( )
I1
(7.2)
Where the subscript 1 refers to the base time when the cost is known, and 2 refers to the time
when the cost is desired. I1 and I2 are the cost index. The index most generally accepted in the
chemical industry is the Chemical Engineering Plant Cost Index (CEPCI). Table 7.2 provides
values for CEPCI from 2001 to 2015.
Table 7.2 Chemical Engineering Plant Cost Index (CEPCI) [44]
Year
Index (I)
2000
394
2001
394
2002
396
2003
402
2004
444
2005
468
2006
500
2007
525
2008
575
2009
521
2010
551
2011
586
2012
585
2013
585
2014
567
2015
567
193
7.4
Bare Module Cost of Equipment at Base Conditions
The capital cost for a chemical plant must take into consideration many costs other than the
purchased cost of the equipment. Table 7.3 presents a summary of the costs that must be
considered in the evaluation of the total capital cost of a chemical plant.
Table 7.3 Summary of costs associated with building a new plant [44]
Equipment cost
Direct Project Expenses
Materials required for installation

Labor to install equipment
Insurance and taxes
Indirect Project Expenses
Construction overhead
Contactor expenses
Contingency
Contingency and Fee

Contractor fee
Site development
Auxiliary Facilities
Auxiliary buildings
Off-sites and utilities
Equation (7.3) is used to calculate the bare module cost for each piece of equipment. The bare
module cost is the sum of the direct and indirect costs shown in Table 7.3.
CBM = C0p F
BM
(7.3)
Where CBM is the bare module equipment cost: direct and indirect costs for each unit, C0p the
purchase cost at base conditions (carbon steel construction and ambient temperature), and FBM
is a factor to account for the items in Table 7.3 as well as the specific material of construction
and operating pressure.
For the base conditions, a superscript zero (0) is added to the bare module cost factor and the
bare module equipment cost. Thus C0BM and F0BM refer to the base conditions. The values for
the bare module cost multiplying factors vary between equipment modules.
194
7.5
Bare Module Cost of Equipment at Operating Conditions
In order to estimate bare module costs for equipment at the operating conditions, purchased
costs for the equipment at base case conditions (ambient pressure using carbon steel) must be
available along with the corresponding bare module factor and factors to account for different
operating pressures and materials of construction. These data are made available for a variety
of common gas/liquid processing equipment in Table 10.4. The bare module cost at the
operating conditions is therefore calculated from the following
CBM = C0p F
BM
= C0p (B1 + B2 FP FM )
(7.4)
Where B1 and B2 are obtained from Table 10.4, and FP and FM are factors to account for
pressure and material of construction, respectively. The bare module for ambient pressure and
carbon steel construction C0BM is obtained by setting FP and FM equal to unity.
Table 7.4 Bare module factor parameters [44]
Equipment
Description
B1
B2
Heat Exchanger
Floating head
1.63
1.66
Vessel (Tower)
Vertical
2.25
1.82
Vessel (Reactor)
Vertical
2.25
1.82
Pump
Centrifugal
1.89
1.35
Furnace
Nonreactive
0.00
2.27
Tray
Sieve
1.90
0.00
Vaporizer/Reboiler
U Tube
1.63
1.66
The pressure factor FP for horizontal and vertical process vessels is given by [44]
(P + 1)D
+ 0.00315
2[850 - 0.6(P + 1)]
FP =
0.0063
Where P is the operating pressure in barg and D is the diameter of the vessel in m.
195
(7.5)
The pressure factors, FP, for the remaining process equipment are given by the following
general form
log10 FP = C1 + C2 log10 (P) + C3 [log10 (P)]
(7.6)
Where P is the operating pressure in barg. The values of constants in equation (7.6) for different
equipment are given in Table 7.5. The material factors, FM, are given in Table 7.6.
Table 7.5 Pressure correction factors FP to be used with equations (7.6) and (7.4) [44]
Equipment
Description
C1
C2
C3
Range
Furnace
Nonreactive
0.1017
-0.1957
0.0940
P > 10
Heat Exchanger
Floating head (shell)
0.0388
-0.1127
0.0818
P>5
Heat Exchanger
Floating head (tube)
-0.0016
-0.0063
0.0123
P>5
Vertical Vessel
Distillation/absorber
Equation (10.5)
Reactor
Packed bed
Equation (10.5)
Tray
Sieve
N/A
Pump
Centrifugal
-0.3935
0.3957
-0.0023
P > 10
Table 7.6 Material correction factors FM to be used with equation (7.4) [44]
Equipment
Description
MOC
FM
Furnace
Nonreactive
Alloy steel tubes
1.10
Heat Exchanger
Floating head/U Tube
Shell CS/Tube CS
1.00
Heat Exchanger
Floating head
Shell CS/Tube SS
1.81
Vessel (Tower)
Vertical
Carbon steel
1.00
Vessel (Reactor)
Horizontal
Stainless steel
3.11
Tray
Sieve
Stainless steel
N/A
Pump
Centrifugal
Carbon steel
1.55
196
7.6
Grassroots Cost
It is necessary to account for other costs in addition to the direct and indirect costs. The term
grassroots (or green field) refers to a completely new facility in which the construction is started
on essentially undeveloped land, a grass field. The grassroots cost takes into consideration all
the four elements shown in Table 10.3. The grassroots cost can be evaluated from [44]
n
CGR = 1.18 CBM,i + 0.50 C0BM,i

i=1
(7.7)
i=1
As mentioned previously, C0BM is the bare module cost at base conditions (carbon steel
construction and ambient pressure).
7.7
Calculations
The calculations presented here are based on the equipment previously designed. These include
the following: four heat exchangers (E-302 through E-305), one distillation column (T-303),
one absorption column (T-302), and one reactor. To account for the remaining equipment, the
grassroots cost will be multiplied by a factor of 1.2.
7.7.1 E-302
E-202 is a floating head heat exchanger with heat transfer area A equal to 889.18 m2. By using
equation (7.1) and Table 7.1, the purchased equipment cost at the base conditions is calculated
log10 C0p (2001) = 4.8306 - 0.2503 log10 (889.18) + 0.3187[log10 (889.18)]
C0p (2001) = $146,880.76

From Table 7.4, B1 = 1.63 and B2 = 1.66. By setting FP and FM in equation (7.4) equal to unity,
we obtain the bear module cost at base conditions
C0BM (2001) = 146,880.76 (1.63 + 1.66) = $483,237.70
197
The bear module cost at the operating conditions is calculated by substituting the operating
correction factors into equation (7.4). Since the pressure is less than 5 barg for both sides (tube
and shell), the pressure correction factor will be equal to unity. That is,
FP = 1.000
The material correction factor FM for shell CS/tube SS is found from Table 7.5
FM = 1.810
CBM (2001) = 146,880.76 (1.63 + 1.66 1.000 1.810) = $680,733.57
Remember that E-302 is four heat exchangers in parallel, each with the same capacity.
Therefore,
CBM (2001) = 4 680,733.57 = $2,722,934.28
10.7.2 E-303
E-303 is a U-tube heat exchanger with heat transfer area A equal to 78.46 m2. The same process
described in section 7.7.1 is used to calculate the purchased equipment cost at the base
conditions
log10 C0p (2001) = 4.8306 - 0.8509 log10 (78.46) + 0.3187[log10 (78.46)]
C0p (2001) = $23,039.80

The bear module cost at the base conditions is calculated in a similar manner to that given in
section 7.7.1
C0BM (2001) = 23,039.80 (1.63 + 1.66) = $75,800.93
198
Since the pressure is less than 5 barg for both sides (tube and shell), the pressure correction
factor will be equal to unity. That is,
FP = 1.000
The material correction factor FM for shell CS/tube SS is the same as that of E-302
FM = 1.810
Hence the bear module cost at the operating conditions is equal to
CBM (2001) = 23,039.80 (1.63 + 1.66 1.000 1.810) = $106,780.25
7.7.3 E-304
E-304 is a floating head heat exchanger with heat transfer area A equal to 262.00 m2. The same
process described in section 7.7.1 is used to calculate the purchased equipment cost at the base
conditions
log10 C0p (2001) = 4.8306 - 0.8509 log10 (262.00) + 0.3187[log10 (262.00)]
C0p (2001) = $43,319.43

section 7.7.1
C0BM (2001) = 43,319.43 (1.63 + 1.66) = $142,520.93
FP = 1.000
The material correction factor FM for shell CS/tube SS is the same as that of E-302
FM = 1.810
199
Hence the bear module cost at the operating conditions is equal to

CBM (2001) = 43,319.43 (1.63 + 1.66 1.000 1.810) = $200,768.24
7.7.4 E-305
E-305 is a floating head heat exchanger with heat transfer area A equal to 26.84 m2. The same
process described in section 7.7.1 is used to calculate the purchased equipment cost at the base
conditions
log10 C0p (2001) = 4.8306 - 0.8509 log10 (26.84) + 0.3187[log10 (26.84)]
C0p (2001) = $18,426.78

section 7.7.1
C0BM (2001) = 18,426.78 (1.63 + 1.66) = $60,624.09
FP = 1.000
The material correction factor FM for shell CS/tube CS is given in Table 7.6 as
FM = 1.000
Hence the bear module cost at the operating conditions is equal to the bear module cost at the
base conditions
CBM (2001) = 18,426.78 (1.63 + 1.66 1.000 1.000) = $60,624.09
200
7.7.5 T-302
The tray absorption column consists of the column itself and the trays within it. For the column
T-302, the volume of the vertical vessel is calculated first
V=
D L = 2.8792 7.800 = 50.777 m3

4
4
By using equation (7.1) and Table 7.1, the purchased equipment cost at the base conditions for
the vertical vessel is calculated
log10 C0p (2001) = 3.4974 + 0.4485 log10 (50.777) + 0.1074[log10 (50.777)]
C0p (2001) = $37,570.86

C0BM (2001) = 37,570.86 (2.25 + 1.82) = $152,913.40
correction factors into equation (7.4). The operating pressure is the same as the base condition
pressure and the column is mainly made of carbon steel. Therefore,
CBM (2001) = C0BM (2001) = 37,570.86 (2.25 + 1.82) = $152,913.40
The trays are calculated individually as any other equipment. For T-302, the tray area is 6.51
m2. By using equation (7.1) and Table 7.1, the purchased equipment cost at the base conditions
is calculated
log10 C0p (2001) = 2.9949 + 0.4485 log10 (6.51) + 0.1074[log10 (6.51)]
C0p (2001) = $2,696.97 per tray
201
From Table 7.4, B1 = 1.90 and B2 = 0.00. Since B2 is equal to zero, the pressure has no effect
on the price of the trays. By applying equation (7.4), we obtain the bare module cost at any
condition
CBM (2001) = C0BM (2001) = 2,696.97 (1.90 + 0.00) = $5,124.24 per tray
Purchased and module cost of the trays are then obtained by multiply the latter calculated price
with the total number of trays, which is 9 trays
CBM (2001) = C0BM (2001) = 9 5,124.24 = $46,118.15 for 9 trays
7.7.6 T-303
The distillation column consists of the column itself and the trays within it. For the column T303, the volume of the vertical vessel is in a similar manner to that discussed in section 7.7.5
V=
2.8602 24.600 = 158.036 m3

4
The purchased equipment cost at the base conditions for the vertical vessel is calculated in a
similar manner as well
log10 C0p (2001) = 3.4974 + 0.4485 log10 (158.036) + 0.1074[log10 (158.036)]
C0p (2001) = $100,640.16

C0BM (2001) = 100,640.16 (2.25 + 1.82) = $409,605.47
correction factors into equation (7.4). Since the distillation column is operating under vacuum,
the correction factor must be taken as [44]
FP = 1.250
202
Since the column is mainly made of carbon steel,

FM = 1.000
The bear module cost at the operating conditions is therefore the following
CBM (2001) = 100,640.16 (2.25 + 1.82 1.250 1.000) = $455,396.75
The trays are calculated individually as any other equipment. For T-303, the tray area is 6.424
m2. By using equation (7.1) and Table 7.1, the purchased equipment cost at the base conditions
is calculated
log10 C0p (2001) = 2.9949 + 0.4485 log10 (6.424) + 0.1074[log10 (6.424)]
C0p (2001) = $2,674.82 per tray

From Table 7.4, B1 = 1.90 and B2 = 0.00. Since B2 is equal to zero, the pressure has no effect
on the price of the trays. By applying equation (7.4), we obtain the bare module cost at any
condition
CBM (2001) = C0BM (2001) = 2,674.82 (1.90 + 0.00) = $5,082.16 per tray
Purchased and module cost of the trays are then obtained by multiply the latter calculated price
with the total number of trays, which is 37 trays
CBM (2001) = C0BM (2001) = 37 5,082.16 = $188,039.97 for 37 trays
7.7.7 R-301
The reactor consists of the vertical shell and the catalyst within it. For the reactor R-201, the
volume is 2.56 m3. By using equation (7.1) and Table 7.1, the purchased equipment cost at the
base conditions is calculated.
log10 C0p (2001) = 3.4974 + 0.4485 log10 (2.560) + 0.1074[log10 (2.560)]
C0p (2001) = $4,938.60
203
C0BM (2001) = 4,938.60 (2.25 + 1.82) = $20,100.10
correction factors into equation (7.4). Since the reactor pressure is less than 5 barg and greater
than 0 barg, the pressure correction factor should be taken as [44]
FP = 1.000
The material correction factor FM for SS is found from Table 7.5
FM = 3.11
CBM (2001) = 4,938.60 (2.25 + 1.82 1.000 3.11) = $39,065.30
The price of the catalyst is $2.25 per kilogram [45]. The purchased cost of the catalyst is
assumed to be the same as the total module cost or represent most of it. For 2956.8 kg of
catalyst,
C0p (2015) = 2956.8 2.25 = $6,652.80
In order to make the calculations uniform, we hypothetically get this price of catalyst at year
2001 by using equation (7.2)
C0p (2001) = $6,652.80 (397/567) = $4,658.13
7.7.8 Grassroots Cost

After calculating the purchased equipment and bare module costs, a total evaluation of these
costs is to be made by tabulating all the measured costs for each equipment, as shown in Table
7.7.
204
Table 7.7 Purchased and module (at the base and actual conditions) costs of equipment
Equipment
C0p (2001)
E-302 (4)
$146,880.76
680,733.57
483,237.70
E-303
$ 23,039.80
106,780.25
75,800.93
E-304
$ 43,319.43
200,768.24
142,520.93
E-305
$ 18,426.78
60,624.09
60,624.09
T-302
$ 37,570.86
152,913.40
152,913.40
Absorption trays (9)
$ 2,696.97
5,124.24
5,124.24
T-303
$100,640.16
455,396.75
409,605.47
Distillation trays (37)
$ 2,674.82
5,082.16
5,082.16
R-301
$ 4,938.60
39,065.30
20,100.10
Catalyst
$ 4,658.13
4,658.13
4,658.13
Total Cost
$943,357.92
$3,977,298.55
C0BM (2001)
CBM (2001)
$3,033,331.97
Finally, to calculate the grassroots cost at 2001, equation (7.7) is applied as follows
CGR (2001) = 1.18 (3,977,298.55) + 0.50 (3,033,331.97) = $6,209,878.28
This total grassroots cost is corrected to 2015 by using equation (7.2) and Table 7.2
CGR (2015) = $6,209,878.28 (567/397) = $8,869,020.11
As mentioned previously, this grassroots cost only takes into account the equipment previously
designed. To account for the remaining equipment, the grassroots cost will be multiplied by a
factor of 1.2
CGR (2015) = 1.2 8,869,020.11 = $10,642,824.14
Since the plant is built from the scratch, the fixed capital investment is equal to the grassroots
cost
FCI = CGR = $10,642,824.14
205
Part Two
Manufacturing Costs
206
7.8
Introduction
The costs associated with the day-to-day operation of a chemical plant must be estimated before
the economic feasibility of a proposed process can be assessed. In order to estimate the
manufacturing cost, process information provided on the PFD, an estimate of the fixed capital
investment, and an estimate of the number of operators required to operate the plant are all
needed. The fixed capital investment is the same as the grassroots cost defined previously.
Manufacturing costs are expressed in units of dollars per unit time, in contrast to the capital
costs, which are expressed in dollars.
There are many elements that influence the cost of manufacturing chemicals. A list of the
important costs involved, including a brief explanation of each cost, is given in Table 7.8.
Table 7.8 Summary of manufacturing costs associated with a plant [44]
Raw materials
Waste treatment
Utilities
Operating labor
Direct Costs
Direct supervisory
Maintenance and repairs
Operating supplies
Laboratory charges
Patents and royalties
Depreciation
Fixed Costs
Local taxes and insurance

Plant overhead costs
Administration costs
General Expenses
Distribution and selling costs

Research and Development
207
The cost information provided in Table 10.8 is divided into three categories [44]:
Direct Manufacturing Costs (DMC): These costs represent operating expenses that vary with
production rate. When product demand drops, production rate is reduced to less than the design
capacity. At this lower rate, a reduction in the factors making up the direct manufacturing costs
would be expected. These reductions may be directly proportional to the production rate, as for
raw materials, or might be reduced slightly for example, maintenance costs or operating labor.
Fixed Manufacturing Costs (FMC): These costs are independent of changes in production
rate. They include property taxes, insurance, and depreciation, which are charged at constant
rates even when the plant is not in operation.
General Expenses (GE): These costs represent an overhead burden that is necessary to carry
out business functions. They include management, sales, financing, and research functions.
General expenses seldom vary with production level. However, items such as research and
development and distribution and selling costs may decrease if extended periods of low
production levels occur.
The equation used to evaluate the cost of manufacture using these costs becomes:
Cost of Manufacture (COM) = DMC + FMC + GE
(7.8)
The cost of the three categories are obtained from Turtons Analysis, Synthesis and Design of
Chemical Processes [44] and are as follows
DMC = CRM + CWT + CUT + 1.33COL + 0.069FCI + 0.03COM
(7.9)
FMC = 0.708COL + 0.068FCI
(7.10)
GE = 0.177COL + 0.009FCI + 0.16COM
(7.11)
Where CRM is the cost of raw materials, CWT the cost of waste treatment, CUT the cost of
utilities, COL the cost of operating labor, and FCI the fixed capital investment (grassroots cost).
208
The total manufacturing cost can be obtained by adding these three cost categories together
and solving for the total manufacturing cost, COM. The result is
COM = 0.18FCI + 2.73COL + 1.23(CUT + CWT + CRM )
(7.12)
The application of equation (10.12) is dependent upon the calculation of the fixed capital
investment FCI, operating labor costs COL , utility streams costs CUT , waste treatment costs
CWT , and raw materials costs CRM . The calculations of these parameters are given in the next
sections.
10.9 Operating Labor Costs

The technique used to estimate operating labor requirements is based on data obtained from
five chemical companies and correlated by Alkhayat and Gerrard [44]. According to this
method, the operating labor requirement for chemical processing plants is given by equation
(7.13)
NOL = 6.29 + 0.23Nnp
(7.13)
Where NOL is the number of operators per shift and Nnp is the number of nonparticulate
processing steps and includes compression, heating and cooling, mixing, and reaction. In
general, the value of Nnp is given by
Nnp =
Equipment
(7.14)
Compressors
Towers
Reactors
Heaters
Exchangers
The value of NOL in equation (7.13) is the number of operators required to run the process unit
per shift. A single operator works on the average 49 weeks a year (3 weeks time off for
vacation and sick leave), five 8-hour shifts a week. This amounts to:
49 weeks/year 5 shifts/week = 245 shifts/operator/year
209
A chemical plant normally operates 24 hours/day. This requires:

365 days/year 3 shifts/day = 1095 operating shifts/year
The number of operators needed to provide this number of shifts is
1095 shifts/year
= 4.5 operators
245 shifts/operator/year
Four and one-half operators are hired for each operator needed in the plant at any time. This
provides the needed operating labor but does not include any support or supervisory staff. To
estimate the cost of operating labor, the average hourly wage of an operator is required.
Chemical plant operators in Saudi Arabia are relatively highly paid. Data from Sadara give the
average yearly salary of a chemical plant operator in Saudi Arabia at $30,000.00 [46]. This
corresponds to $14.423 for a 2080-hour year.
7.10 Utility Streams Costs

Utility streams, such as cooling water and steam for heating, are necessary for the control of
stream temperatures as required by the process. These utilities can be supplied in a number of
ways.
Purchased from a public or private utility: In this situation no capital cost is involved, and
the utility rates charged are based upon consumption. In addition, the utility is delivered to the
battery limits at known conditions.
Supplied by the company: A comprehensive off-site facility provides the utility needs for
many processes at a common location. In this case, the rates charged to a process unit reflect
the fixed capital and the operating costs required to produce the utility.
Self-generated and used by a single process: In this situation the capital cost for purchase
and installation becomes part of the fixed capital cost of the process unit. Likewise the related
operating costs for producing that particular utility are directly charged to the process unit.
210
Utilities that would likely be used in a chemical plant are shown in Table 7.9. These costs vary
by location, and the costs shown here are based on Saudi Arabia.
Table 7.9 Utilities provided by off-sites [44]
Utility
Description
Cost
Low Pressure Steam
5 barg, 160 C
27.70 $/1000 kg
Deionized Water
For absorption column
1.00 $/1000 kg
Cooling Water
Increase from 25 to 40 C
14.80 $/1000 m3
Electrical Substation
110V / 220V / 440V
0.06 kWh
The approach used to estimate the costs given in Table 7.9 is to assume that the capital
investment required to build a facility to supply the utility for example, a cooling tower, a
steam boiler, and so forth has already been made. This would be the case when a grassroots
cost has been used for the fixed capital investment. The costs associated with supplying a given
utility are then obtained by calculating the operating costs to generate the utility. These are the
costs that have been presented in Table 7.9. Remember that the utility cost is to be multiplied
by 330 days a year, since production is shutdown 35 days a year for maintenance.
7.11 Raw Materials Costs

The cost of raw materials can be estimated by using the current price listed in such publications
as the Chemical Market Reporter. Table 7.10 gives a list of materials along with their selling
prices, as of 2015. Note that the price of low pressure steam is the same as that given in Table
7.9, but is given since it is used in the production process as one of the feeds.
Table 7.10 Raw materials and their selling price [47]
Raw Material
Selling Price
Propylene
0.869
$/kg
Catalyst
2.250
$/kg
Low Pressure Steam
27.70
$/1000 kg
Acetic Acid
0.700
$/kg
211
The acetic acid quantity can be credited and therefore will be treated in the calculations as a
raw material with a minus sign (favorable). Furthermore, the make-up catalyst is quantified as
a raw material. Catalyst make-up is assumed as 10% of the total catalyst weight [44].
7.12 Manufacturing Costs Calculations

7.12.1 Operating Labor
The number of non-particulate processing steps is first evaluated using equation (7.14)
Nnp = 1 reactor + 4 Towers + 1 Compressor + 5 HE = 11
NOL is then calculated by substituting Nnp into equation (7.13)
NOL = 6.29 + 0.23 (11) = 2.970
The number of operators is now calculated using the method described previously
Number of operating labor = (2.970) (4.5) = 13.36 (rounded-up to 14)
Finally the total operating labor cost COL is evaluated by multiplying the yearly salary with the
number of operators as follows
COL = 30,000.00 14 = $420,000.00/year
7.12.2 Utility Streams

The designed equipment along with the corresponding utilities are tabulated in Table 7.11. By
using the utility prices given in Table 7.9, the cooling water CW is equal to
CUT (CW) = (587.622 kg/s)(0.001 m3/kg)($14.8/1000 m3)(330 day/y)(24 h/ day)(3600 s/h)
= $247,963.32/y
Applying the same calculations to the low pressure steam gives the following
CUT (LPS) = (0.909 kg/s)($27.70/1000 kg)(330 day/y)(24 h/day)(3600 s/h) = $717,714.76/y
212
Applying the same calculations to the deionized water used for the absorption tower
CUT (DW) = (1.269 kg/s)($1.00/1000 kg)(330 day/y)(24 h/day)(3600 s/h) = $36,181.73/y
Finally, the total utility cost CUT is obtained by adding up all the calculated utility costs
CUT = 247,963.32 + 717,714.76 + 36,181.73 = $1,001,859.81/y
Proceeding in a similar manner, the utility cost will be multiplied by a factor of 1.2 to account
for the remaining equipment (i.e. the ones without design information)
CUT (20%) = 1.2 1,001,859.81 = $1,202,231.77/y
Table 7.11 Utility usage
Equipment
Electricity kWh
CW kg/s
LPS kg/s
DW kg/s
E-302
559.872
E-303
0.909
E-304
22.440
E-305
5.310
T-302
1.269
Total Usage
0.000
587.622
0.909
1.269
7.12.3 Raw Materials

The propylene consumed in the plant is obtained from the material balance sheet and is equal
to 9619.488 kg/h. By using the prices in Table 7.10, the propylene yearly cost is calculated
CRM (Propylene) = (9619.488 kg/h)($0.869/kg)(330 day/y)(24 h/day) = $66,205,933.77/y
It was assumed that the catalyst make-up is 10% of the total catalyst weight. Therefore,
Catalyst makeup =
2956.80 0.1
= 0.037 kg/h
330 24
213
By using the price in Table 7.10, the catalyst make-up cost is calculated
CRM (Catalyst) = (0.037 kg/h)($2.250/kg)(330 day/y)(24 h/day) = $665.28/y
The LPS consumed in the plant is equal to 32150.52 kg/h. By using the prices in Table 7.10,
the LPSS yearly cost is calculated
CRM (LPS) = (32150.52 kg/h)($27.70/1000 kg)(330 day/y)(24 h/day) = $7,053,309.68/y
Furthermore, the acetic acid (652.80 kg/h) in the distillations overhead is sold. The cost of raw
material is therefore calculated with a negative sign
CRM (Acetic Acid) = (-1)(652.80 kg/h)($0.700/kg)(330 day/y)(24 h/day) = $(3,619,123.20)/y
Finally, the total utility cost CUT is obtained by adding up all the calculated utility costs
CUT = 66,205,933.77 + 665.28 + 7,053,309.68 - 3,619,123.20 = $69,640,785.53/y
7.12.4 Total Manufacturing Costs

After evaluating the operating labor, utility and raw material costs, the total manufacturing
costs is obtained by applying equation (7.12)
COM = (0.18)(10,642,824.14) + (2.73)(420,000.00) + (1.20)(1,202,231.77 + 0.00 +
69,640,785.53)
= $90,199,219.62/y
It is more representative to give the manufacturing costs in terms of the production capacity.
For a production capacity of 89,211.35 ton/y of acrylic acid
COM = ($90,199,219.62/y)/(89,211.35 ton/y)
COM = $1,011.07/kg acrylic acid
This manufacturing price is extremely important to set the lower limit of the product selling
price in the succeeding section.
214
Part Three
Profitability Analysis
215
7.13 Selling Price

The selling price is determined based on the manufacturing cost evaluated in dollars per ton of
acrylic acid produced. The revenue at each year is then determined from the following relation
Revenue = Production Rate Selling Price
(7.15)
This selling price must give a reasonable revenue which will give a proper net profit within the
expected limits. Therefore, a selling price for the manufacturing cost of $1,010.40 / 1000 kg
acrylic acid must be greater than this price.
7.14 Project Life

In order to do the economic analysis of any project, a project life must be determined by the
corporation implementing the project. In our case, a ten-year project with two years at the
beginning to build-up the plant is chosen. It should be noted that most projects lives are taken
around this region.
7.15 Cash Flow and Interest Rate

The pillar of the project economic analysis is to determine the cash flow into and out of the
system using a plus sign for any income and a minus sign for the costs. There are two types of
cash flow:
Discrete cash flow
Cumulative cash flow
Discrete cash flow gives the income and costs of each year separately from any other years,
where the cumulative cash flow gives a total price of the project value at any year (for year
three all the cash flow before this year is added up to give the cumulative form).
In cumulative cash flow, the time value of money must be taken under consideration that it is
not possible to add up the cash flows with different years of occurrence without shifting all the
values to the present value (in our case) using a discounted rate of interest that is subjected by
the bank or the investor supplying the project.
216
The following equation is applicable whenever a cash value is to be shifted to present

P = F(1 + i)- n
(7.16)
P is the present shifted value through year n which has a cash value of F
7.16 Taxation and Depreciation

Any profitable project with net profit value greater than zero must be charged with a taxation
cut as a percentage of the net profit by the government or the responsible legitimation entity.
In our case, this interest rate is equal to 2.5% and is charged by the Department of Zakat and
Income Tax.
It is unfair to charge a taxation cut on the profit without taking into consideration the capital
investment cost of the project. It sometimes happens that even for a positive project yearly
flow, the final outcome is a total loss. Therefore the taxation rate will be taken after subtracting
the profit with depreciation. The final profit after taxation will be given as follows
Net Profit After Taxation = (R - COMd - d)(1 - t)
(7.17)
Then by adding back the depreciated value to the net profit, the final cash flow after taxation
is obtained as the following
After Tax Cash Flow = (R - COMd - d)(1 - t) + d
(7.18)
Where d is the depreciation value of the fixed capital investment. This depreciation value
differs based on the deprecation period, the method to be used, and the salvage value S. The
depreciated value is only the fixed capital investment without land (FCIL). This is equal to the
fixed capital investment obtained from previous calculation of the grassroots cost with the land
price subtracted out of it. This land price is assumed to equal 10% of the FCI L (without
depreciation). Based on this, a total fixed capital investment can be defined as
Total Fixed Capital Investment = FCIL + Land + WC
217
(7.19)
Where WC is the working capital that is required to run the plant in the first year. This working
capital investment is usually taken as 20% of FCIL. The three typical methods used in
depreciation are:
Straight Line Deprecation Method , SL
Sum of Years Digits Depreciation Methods, SOYD
Double Declining Balance Depreciation Method, DDB
Each one has its own formula to give the depreciated value. However, in this context the
straight line deprecation method will be used for its convenience. This depreciated value is
charged equally each year of the depreciation period. This is illustrated by equation (7.20).
dSL
k =
[FCIL - S]
n
(7.20)
Note that n here does not represent the depreciation period set by the Department of Zakat and
Income, rather represent the project life.
7.17 Cash Flow Diagram for a New Project

A table of the cash flow is obtained by tabulating all the investment as minus value and
calculating all the net profit after taxation to evaluate the discrete project value at each year.
This is then added cumulatively to be plotted as shown in Figure 7.1.
Figure 7.1 A typical cumulative cash flow diagram
218
Figure 7.1 shows a typical cash flow diagram for a new ten-year-life project. At the beginning,
the land is added as a minus flow with FCIL divided into payments over the first two years. At
the end, the land, working capital and salvage value are added back with a positive values.
7.18 Profitability Criteria for Project Evaluation

In order to make economic analysis to the project, different criteria are to be measured to give
more comprehensible tools for evaluation. Consequently, there are three bases used for the
evaluation of profitability:
Time
Cash
Interest rate
Based on these criteria, discounted and non-discounted techniques might be considered. Nondiscounted technique does not take into account the time value of money, where the other
technique does shift the cash values to the present value by using equation (10.16). Time, cash,
interest rate are explained and subjected to a formulated value for both the discounted and
non-discounted bases in the following context.
7.18.1 Non-discounted Profitability Criteria

The non-discounted profitability criteria for time, cash and interest rate is shown in Figure 10.2.
Figure 7.2 Non-discounted profitability criteria
219
The term used to manifest this criterion is the payback period, PBP. Payback period is the time
required to recover the FCIL after the start-up of the project. This is illustrated in Figure 7.2.
Apparently, a shorter PBP indicates a profitable project.
Furthermore, the term used in describing the cash criterion is the cumulative cash position
(CCP). This is the project worth (value) at the end of the project life.
For the interest rate criterion, the term used is the rate of return on investment (ROROI).
ROROI describes the non-discounted rate at which money is made from a fixed capital
investment, and is equal to:
ROROI =
Average annual net profit

Fixed capital investment
(7.21)
This average net profit is based on the project life from the start-up
7.18.2 Discounted Profitability Criteria

The discounted profitability criteria takes into account the time value of money. For the time
criterion, the discounted payback period is used as a replacement of PBP. The DPBP is the
time required to recover FCIL after shifting all the value to the present point using equation
(7.16).
Furthermore, the term used in describing the cash criterion is the discounted cumulative cash
position or can be known as the net present value (NPV) of the project. This is the projects
worth (value) at the end of the project life after taking into account the time value of money.
For the interest rate criterion, the term used is the discounted cash flow rate of return
(DCFROR). DCFROR is the discounted rate at which the NPV is equal to zero at the end of
project.
7.19 Analysis and Calculations

The fixed capital investment without land is first evaluated.
FCIL = $10,642,824.14/1.1 = $9,675,294.67
220
For a land price of 10% the FCIL,

Land = $10,642,824.14/11 = $967,529.47
Then for a working capital equal to 20% the FCIL, the following is applied:
Working Capital = $9,675,294.67 (0.20) = $1,935,058.93
The depreciation is assumed to be over a period equal to 9.5 (typical value used). By using
equation (7.20) for a salvage value of zero,
dSL
k =
9,675,294.67
= $ 1,018,452.07
9.5
The project life was selected to be ten years with two years of construction. The land payment
is set to be at time zero, where the FCIL is divided into two payment. At the end of the first
year, a payment of $6,500,000.00 is paid, and the rest is delivered at the end of the second year.
The working capital is then paid at the end of the second year along with the second payment
to start up the project in the beginning of year three. In the following context, three cases of
three different selling prices will be analyzed.
7.19.1 Case One
The selling price is first selected to be 3.9% greater than the manufacturing costs. This
corresponds to a selling price of $1050/1000 kg of acrylic acid. By using equation (7.15), the
following is obtained,
Revenue = 89,211,35 1050 = $93,671,913.81/year
Then by tabulating the cash flows along with the depreciation values, as shown in Table 7.12,
and using the equations from (7.16) to (7.20), the cumulative cash flow can be plotted for both
the discounted and non-discounted cash flow by setting the interest rate equal to 12%. Figure
7.3 shows the non-discounted cumulative worth and Figure 7.4 shows the discounted
cumulative worth.
221
C o s t a n d P r o f i t a b i l i t y A n a l ys i s
Table 7.12 Profitability analysis for a selling price of $1050/1000 kg of acrylic acid and an interest rate of 12% (all values in million dollars)
Years
Invest
dk
FCIL - Sdk
COMd
Profit
DCF
Non-Disc
DCF
Disc
CCF Disc
CCF
Non-Disc
(0.968)
9.675
(0.968)
(0.968)
(0.968)
(0.968)
(6.500)
9.675
(6.500)
(5.804)
(6.771)
(7.468)
(3.175)
9.675
(3.175)
(2.531)
(9.302)
(10.643)
(1.935)
9.675
(1.935)
(1.543)
(10.845)
(12.578)
1.018
8.657
93.672
90.199
3.411
3.411
2.428
(8.417)
(9.167)
1.018
7.638
93.672
90.199
3.411
3.411
2.168
(6.249)
(5.755)
1.018
6.620
93.672
90.199
3.411
3.411
1.936
(4.313)
(2.344)
1.018
5.601
93.672
90.199
3.411
3.411
1.728
(2.585)
1.067
1.018
4.583
93.672
90.199
3.411
3.411
1.543
(1.042)
4.479
1.018
3.565
93.672
90.199
3.411
3.411
1.378
0.336
7.890
1.018
2.546
93.672
90.199
3.411
3.411
1.230
1.566
11.301
10
1.018
1.528
93.672
90.199
3.411
3.411
1.098
2.664
14.713
11
1.018
0.509
93.672
90.199
3.411
3.411
0.981
3.645
18.124
12
1.018
93.672
90.199
3.411
3.411
0.876
4.521
21.535
12
2.903
2.903
0.745
5.266
24.438
222
Non-Discounted Cumulative Worth
Non-discounted Project Worth

27.000
24.000
21.000
18.000
15.000
12.000
9.000
6.000
3.000
(3.000) 0
(6.000)
(9.000)
(12.000)
(15.000)
10
11
12
13
End of Years
Figure 7.3 Non-discounted project worth along the project life
From Figure 7.3, the PBP is equal to 2.84 years, and the cumulative cash position is equal to
$24.438 million. The ROROI is then measured by using equation (7.21)
ROROI =
(3.411 10 + 2.903) / 10 1
= 28.258 %
9.675
10
Discounted Cumulative Worth
Discounted Project Worth

7.500
6.000
4.500
3.000
1.500
(1.500) 0
(3.000)
(4.500)
(6.000)
(7.500)
(9.000)
(10.500)
(12.000)
10
11
12
13
End of Years
Figure 7.4 Discounted project worth along the project life
From Figure 7.4, the DPBP is equal to 4.05 years, and the net present value NPV is equal to
$5.266 million. The DCFROR is obtained by setting NPV equal to zero using Excel
Spreadsheet to give a rate of 20.777%. Table 10.13 shows the evaluated criterion for both the
discounted and non-discounted bases.
223
Table 7.13 Criterion summary for first case

Non Discounted Criterion
CCP (Million Dollars)
24.44
ROROI
28.258%
PBP ( years)
2.84
Discounted Criterion
NPV (Million Dollars)
5.27
DCFROR
20.777%
DPBP ( years)
4.05
7.19.2 Case Two

For the second case, the selling price is selected to be 6.8% greater than the manufacturing
costs. This corresponds to a selling price of $1080/1000 kg of acrylic acid. By using equation
(7.15), we obtain the following
Revenue = 89,211.35 1080 = $96,348,254.21/year
Table 7.15 shows the profitability analysis for a selling price of $1080/1000 kg of acrylic acid
and is obtained by using the same procedure discussed in the first case. The cumulative cash
flow is then plotted for both the discounted and non-discounted cash flow by setting the interest
rate to 12%, as shown in Figure 7.5 (non-discounted) and Figure 7.6 (discounted). Table 7.14
shows the evaluated criterion for both the discounted and non-discounted bases.
Table 7.14 Criterion summary for second case
50.53
ROROI
55.228%
PBP ( years)
1.61
17.02
DCFROR
36.716%
DPBP (years)
2.11
224
Table 7.15 Profitability analysis for a selling price of $1080/1000 kg of acrylic acid and an interest rate of 12% (all values in million dollars)
Years
Invest
dk
FCIL - Sdk
COMd
Profit
DCF
Non-Disc
DCF
Disc
CCF Disc
CCF
Non-Disc
(0.968)
9.675
(0.968)
(0.968)
(0.968)
(0.968)
(6.500)
9.675
(6.500)
(5.804)
(6.771)
(7.468)
(3.175)
9.675
(3.175)
(2.531)
(9.302)
(10.643)
(1.935)
9.675
(1.935)
(1.543)
(10.845)
(12.578)
1.018
8.657
96.348
90.199
6.021
6.021
4.285
(6.560)
(6.557)
1.018
7.638
96.348
90.199
6.021
6.021
3.826
(2.733)
(0.536)
1.018
6.620
96.348
90.199
6.021
6.021
3.416
0.683
5.484
1.018
5.601
96.348
90.199
6.021
6.021
3.050
3.733
11.505
1.018
4.583
96.348
90.199
6.021
6.021
2.723
6.457
17.526
1.018
3.565
96.348
90.199
6.021
6.021
2.432
8.889
23.547
1.018
2.546
96.348
90.199
6.021
6.021
2.171
11.060
29.568
10
1.018
1.528
96.348
90.199
6.021
6.021
1.939
12.998
35.588
11
1.018
0.509
96.348
90.199
6.021
6.021
1.731
14.729
41.609
12
1.018
96.348
90.199
6.021
6.021
1.545
16.274
47.630
12
2.903
2.903
0.745
17.019
50.532
225

56.000
52.000
48.000
44.000
40.000
36.000
32.000
28.000
24.000
20.000
16.000
12.000
8.000
4.000
(4.000) 0
(8.000)
(12.000)
(16.000)
10
11
12
13
End of Years
The second case shows that by adding thirty dollars to the selling price, the profit becomes
irrationally high with a really short PBP that is equal to 1.61 years. This additional price will
effect adversely on the marketing of the product (less attractive to the costumers).

20.000
18.000
16.000
14.000
12.000
10.000
8.000
6.000
4.000
2.000
(2.000) 0
(4.000)
(6.000)
(8.000)
(10.000)
(12.000)
(14.000)
10
End of Years
226
11
12
13
7.19.3 Case Three

For the third case, the selling price is selected to be 1.60 % greater than the manufacturing
costs. The corresponding selling price is $1036.56/1000 kg of acrylic acid. By using equation
(7.14), we obtain the following
Revenue = 89,211.35 1036.56 = $92,472,895.20/year
Table 7.17 shows the profitability analysis for a selling price of $1036.56/1000 kg of acrylic
acid and is obtained by using the same procedure discussed in the first case. The cumulative
cash flow is then plotted for both the discounted and non-discounted cash flow by setting the
interest rate equal to 12%, as shown in Figure 7.7 (non-discounted) and Figure 7.8 (discounted).
Table 7.16 shows the evaluated criterion for both the discounted and non-discounted bases.
Table 7.16 Criterion summary for second case
12.75
ROROI
16.175%
PBP ( years)
4.31
0.00
DCFROR
12.000 %
DPBP (years)
7.25
227
Table 7.17 Profitability analysis for a selling price of $1036.56/1000 kg of acrylic acid and an interest rate of 12% (all values in million dollars)
Years
Invest
dk
FCIL - Sdk
COMd
Profit
DCF
Non-Disc
DCF
Disc
CCF Disc
CCF
Non-Disc
(0.968)
9.675
(0.968)
(0.968)
(0.968)
(0.968)
(6.500)
9.675
(6.500)
(5.804)
(6.771)
(7.468)
(3.175)
9.675
(3.175)
(2.531)
(9.302)
(10.643)
(1.935)
9.675
(1.935)
(1.543)
(10.845)
(12.578)
1.018
8.657
92.473
90.199
2.242
2.242
1.596
(9.249)
(10.336)
1.018
7.638
92.473
90.199
2.242
2.242
1.425
(7.824)
(8.093)
1.018
6.620
92.473
90.199
2.242
2.242
1.272
(6.552)
(5.851)
1.018
5.601
92.473
90.199
2.242
2.242
1.136
(5.416)
(3.609)
1.018
4.583
92.473
90.199
2.242
2.242
1.014
(4.401)
(1.366)
1.018
3.565
92.473
90.199
2.242
2.242
0.906
(3.496)
0.876
1.018
2.546
92.473
90.199
2.242
2.242
0.809
(2.687)
3.118
10
1.018
1.528
92.473
90.199
2.242
2.242
0.722
(1.965)
5.360
11
1.018
0.509
92.473
90.199
2.242
2.242
0.645
(1.321)
7.603
12
1.018
92.473
90.199
2.242
2.242
0.576
(0.745)
9.845
12
2.903
2.903
0.745
0.000
12.748
228
C h a p t e r S e v e n : C o s t a n d P r o f i t a b i l i t y An a l y s i s

16.000
14.000
12.000
10.000
8.000
6.000
4.000
2.000
(2.000) 0
(4.000)
(6.000)
(8.000)
(10.000)
(12.000)
(14.000)
10
11
12
13
11
12
13
End of Years

1.000
(1.000) 0
(2.000)
(3.000)
(4.000)
(5.000)
(6.000)
(7.000)
(8.000)
(9.000)
(10.000)
(11.000)
(12.000)
10
End of Years
Figure 7.8 shows that selling the product below $1036.56/1000 kg of acrylic acid with an
interest rate of 12.00% will result in a final loss. Consequently, if it is required to lower the
price below that breakeven point, a reduction in the interest rate is requested to balance the
situation.
7.19.4 Selling Price Analysis
After determining the profitability criteria for three different selling prices, a selling price is
selected based on a rational payback period and a discounted payback period with a reasonably
attractive net present value (see Figure 7.9).
229
C h a p t e r S e v e n : C o s t a n d P r o f i t a b i l i t y An a l y s i s
Selling Price Effects on DPBP and PBP

8.00
Cash Back (Year)
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
1030.00 1035.00 1040.00 1045.00 1050.00 1055.00 1060.00 1065.00 1070.00 1075.00 1080.00 1085.00
Selling Price $/1000 kg

PBP
DPBP
Figure 7.9 Selling price effects on DPBP and PBP.
Figure 7.9 shows that a selling price of $1050 has a reasonable payback period within the
typical range of 2 to 4 years. However, a price below $1037 will give a very long payback. A
price greater than $1060 will give a slightly shorter payback period. As a result, the first case
(selling price of $1050) is selected as the selling price for a discounted interest rate of 12%.
For the NPV and selling price value, a visual representation of the effects of the selling price
on the net present value is illustrated in Figure 7.10.
NPV
18.00
16.00
NPV $ in Million
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
1030.00 1035.00 1040.00 1045.00 1050.00 1055.00 1060.00 1065.00 1070.00 1075.00 1080.00 1085.00
Selling Price $/1000 kg
Figure 7.10 Effects of the selling price on the net present value
230
Ch a p te r E ig h t: S i te Lo c a tio n a nd P la n t La yo u t
CHAPTER EIGHT
Site Location and Plant Layout
8.1
Site Location
8.1.1 Introduction
The location of the manufacturing plant is an essential part that must be taken into
consideration. The site must be suitable for future expansion. In general, the location of the
plant depends on many criteria, such as: the availability of raw materials, the availability of
products distribution chain, and the availability of land and infrastructure. In addition, site
location also plays an important role in the profitability and success of the operation for the
estimated lifetime of the plant.
It is necessary to consider the already available industrial regions within Saudi Arabia. But yte
following factors must be considered first:
Raw materials availability
The acrylic acid plant should be built close to the raw materials supplier. Selecting the closest
location to the supplier will reduce the transportation cost of raw materials to the plant in the
sense that the plant will require a daily input of raw materials throughout the year. If the needed
raw materials are to be imported, it would be important to consider a location near to a seaport
with excellent infrastructure.
Marketability
The proposed plant site should ideally be located close to the primary market in order to
minimize transportation costs. The local demand of the product should also be taken into
consideration in selecting a suitable plant site. It would be best if the raw material supplier and
also the buyers are nearby.
231
Utilities
Utilities supply is a need for every plant. Utilities provide the supply of electricity, industrial
gases and other utilities such as steam and water. These utilities are used to run the process in
the plant. The utilities supply must be sufficient and reliable in order to have the plant running
smoothly. Power and steam requirements are high in most industrial plants, and fuel is
ordinarily required to supply these utilities.
Land availability and cost
The cost of the land depends on the location selected. An economical land price would be ideal
so as to reduce the total investment cost. It is important to choose the lowest land price when
starting a new plant to gain the highest economic value.
Transportation facilities
Water, railroads, and highways are the common means of transportation used by major
industrial concerns. The kind and amount of products and raw materials determine the most
suitable type of transportation facilities. In any case, careful attention should be given to local
freight rates and existing railroad lines. The proximity to railroad centers and the possibility of
canal, river, lake, or ocean transport must be considered. If possible, the plant site should have
access to all three types of transportation; at least two types should be available.
Waste disposal
A good industrial site is when it is provided with a good waste and disposal facility. If there
are none, then the best way is to choose the area which is the nearest to this facility. This factor
is not of great concern when the plant is to be built with a treatment unit.
Labor supply
The plant should be located where sufficient labor supply is available. Skilled construction
workers will usually be brought in from outside local area but there should be an adequate pool
of unskilled workers available locally and workers suitable for training to operate the plant.
Available, inexpensive manpower from the surrounding area will contribute in reducing the
cost of operation.
232
Taxation and legal restrictions
State and local tax rates on property income, unemployment insurance and similar items vary
from one location to another. Similarly, local regulations on zoning, building codes, nuisance
aspects, and transportation facilities can have a major influence on the final choice of a plant
site. In fact, zoning difficulties and obtaining many required permits can often be much more
important in terms of cost and time delays than many of the factors discussed previously [1].
8.1.2 Overview of Possible Sites

A production plant for the manufacturing of acrylic acid is categorized as a petrochemical
project. The plant must therefore be sited in a place where the previously discussed factors are
available. In Saudi Arabia, there are two locations that satisfy these requirements: Jubail
Industrial City (on the east coast) and Yanbu Industrial City (on the west coast).
Jubail Industrial City
The Jubail Industrial City is one of the most modern and biggest industrial complexes in Asia.
Construction operations in the city were stepped up in 1975. Jubail Industrial City comprises a
group of major companies which produce petrochemicals, chemical fertilizers, industrial gases,
steel, iron and oil. Jubail industrial city has been divided into five zones [2]:
i.
The industrial zone has nineteen main factories with 136 ancillary installations. These
factories produce steel, aluminum, plastic and fertilizers. All operations are under the
direct supervision of the Saudi Basic Industries Corporation (SABIC). This zone covers
an area of 8,000 hectares, or approximately eighty kilometers. In catering to diverse
needs, SABIC leases fully developed and fully equipped industrial sites at nominal
rents.
ii.
The residential area is composed of eight localities built on an adjacent island linked to
the mainland. There are 40,000 inhabitants. The area has the capacity to accommodate
375,000 people in modern up-to-date houses.
iii.
The airport area, covering an area of 250 kilometers, has the capacity to receive all
types of aircraft and handles the transportation of passengers and freight.
233
iv.
The picnic zone, situated to the west of the industrial zone, covers an area of 204
kilometers. To the residents of the city, it is an invaluable recreation area. It
encompasses verdant sites, playgrounds and facilities for water sports. The zone is set
among abundant trees and rare plants.
v.
Al-Batwah Island is affiliated with Jubail Industrial City. A picnic site with a park and
a zoo, it features plant nurseries, fishing sites and a marina.
Yanbu Industrial City
The new industrial city of Yanbu was planned as the spearhead for the modernization of the
whole of Saudi Arabia's rural north-western coastal region. It would also provide a new
strategic outlet on Red Sea shipping lanes, to handle most of the Kingdom's sea-borne trade.
Planners envisaged a city with housing and lifestyle facilities second to none, and an urban
population, which would exceed 100,000 by the year 2020 [3].
The Royal Commission planned 14 neighborhoods, or residential districts in the new city,
which was to be known as Yanbu Industrial City. After an initial injection of government
money, the strategy was to provide incentives for increasing private investment. The Royal
Commission sought to achieve this by the establishment of functioning primary and support
industries, and by building an attractive residential environment for both management and
workforce [4].
The Commission's first priority was therefore to establish a physical infrastructure, capable of
supplying the needs of this growing urban community. Yanbu is currently host to 15 heavy
hydrocarbons, petrochemical and mineral facilities as well as 30 light manufacturing and
support industries. There are many big industries in the pipeline at various stages of
construction. In Yanbu, the world-class refining and petrochemical complexes convert oil and
natural gas into products for export and into feedstock for local manufacturers [3].
8.1.3 Site Selection

After discussing the two possible locations, Jubail Industrial City and Yanbu Industrial City,
what is left is the final selection of the plant location between these two.
234
To do so, the multiple-criteria decision analysis method will be used. Note that this is the same
method that was used in chapter three to select the best production process. Table 8.1 shows
the guidelines upon which the decision analysis will be based on. The final table summarizing
the results is given in Table 8.2.
Table 8.1 Site location guidelines
Factors
8 - 10 Marks
4 - 7 Marks
Heavy or
0 - 3 Marks
Light or
Type of industry
Heavy industry
Petrochemical
Raw materials
Own country
Pipeline system
Utilities
Electrical supply
Water supply
Steam supply
Electrical supply
Water supply
Low cost of
Medium tariff of
High of cost of
electric Supply
Low of cost of
water supply
electric supply
Medium cost of
water supply
High of cost of
Land area > 60
Land area < 60
Land area < 30
Price of utilities
Available area
intermediate
industry
intermediate
industry
Outside country
Outside country
(distance < 60 km)

Pipeline system
Pipeline system
hectares
hectares
(distance > 60 km)
Less electrical
supply
Less water supply

electric supply
water supply
hectares
Room for
Expansion
High
Medium
Low
Cost of living
Low
Medium
High
Roads and
Acceptable roads
highways
Near to port
Near to port
Roads and
Transportation
highways
Near to port
Railway system
235
and highways
Services for industrial

accidents
Available
Training centers
Available
Somewhat
None
available
Somewhat
None
available
Table 8.2 Final site selection results

Site Location
Factors
Yanbu
Jubail
Type of industrial area
10
Raw materials
10
Power
Water
Steam
Natural gas
Available area
Land price
Room for expansion
Cost of living
Seaport
Railway
Roadway
10
10
Airport
Power
Water
Services for industrial accidents
10
10
Training centers
10
Total Score
140/180
149/180
Utilities
Transportation
Price of Utilities
236
Hence it can be seen from Table 8.2 that Jubail Industrial City received the highest total points
(scoring 149 out of a possible 180) and thus it will be selected as the most suitable site for
constructing an acrylic acid plant. Figure 8.1 shows a satellite image of Jubail Industrial City.
Figure 8.1 Location of Jubail Industrial City.
8.2
Plant Layout
Plant Layout is the physical arrangement of equipment and facilities within a plant. Optimizing
the layout of a plant can improve productivity, safety and quality of products. Unnecessary
efforts of materials handling can be avoided when a suitable plant layout is engineered.
The process unit and ancillary buildings should be laid out to give the most economical flow
of materials and personnel around the site. Hazardous processes must be located at a safe
distance from other buildings. Consideration must also be given to future expansion of the site.
237
The ancillary buildings and services required on a site in addition to the main processing units
include the following:
Storage for raw materials and products
Maintenance workshops
Stores, for maintenance and operating supplies
Laboratories for process quality control
Fire station and other emergency services
Utilities: steam boilers, compressed air , power generation, refrigeration,
transformer station
Collection
Offices for general administration
Canteens and other amenity buildings
Parking lots
When roughing out the preliminary site layout, the process units are normally sited first and
arranged to give a smooth flow of raw materials. Process units are usually spaced at least 30 m
apart; grater spacing may be needed for hazardous processes. The location of the ancillary
buildings should be arranged so that the time spent by personnel in travelling between buildings
is minimized.
The administration and laboratory buildings, in which a relatively large number of people will
be working, should be located away from potentially hazard processes. Control rooms are
normally located adjacent to the processing units, but it may be sited at a safer distance for
hazard process.
Utility buildings should be sited to give the most economical run for pipes to and from the
processing units. The main storage areas should be placed between loadings and unloading
facilities. Storage tanks containing hazardous materials should be sited at least 70 m from the
site boundary.
238
There are several factors to consider before proposing an acrylic acid plant layout, the
following are a few:
Cost
Minimization of construction cost is done by adopting the shortest run of connecting pipes
between equipment. The cost is also reduced by having the least amount of structural steel
work. The most important thing is to have an arrangement that suits operation and maintenance.
Operation
Equipment such as valves, sample points and instruments that are frequently attended must be
located near to the control room, with convenient positions and heights to ease the operators
job. In addition, sufficient working and headroom space must be provided to allow easy access
to equipment.
Maintenance
The following considerations have been taken into account in laying out the acrylic acid plant:
the reactor will be placed in an open space to allow for removing or replacing the catalysts,
enough space will be allocated for heat exchangers to allow for withdrawing the bundles, and
all equipment will be accessible to cranes/lift trucks
Safety
Several safety factors have been taken into consideration in laying out the acrylic acid plant,
the following are a few examples: Operators will have four escape routes in the event of an
emergency, hazardous handling processes are separated from each other, elevated areas will
have at least one stairway, and flammable materials will be located at a safe distance from the
main process area.
Plant expansion
Equipment will be arranged in a way such that sufficient room is available for future
expansions.
Figure 8.2 shows the final proposed acrylic acid plant layout
239
C ha p te r E i ght: S i te Loc a ti on a nd P la nt La yo u t
Figure 8.2 Final proposed acrylic acid plant layout
240
Conclus ions
Commented [HA7]:
Conclusions
241
Recommendations
Commented [HA8]:
Recommendations
242
Re ferences
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]
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]
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Organization, 1997.
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]
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Report," 2013.
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[Online]. Available: http://www.sozogaku.com/fkd/en/cfen/CC1000126.html. [Accessed

27 February 2015].
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[38 S. Kaka, Heat Exchangers: Selection, Rating and Thermal Design, CRC Press, 2002.
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[39 E. A. Saunders, Heat Exchanges: Selection, Design and Construction, Longman Scientific
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and Technical, 1988.
[40 "Session 3 Design of Heat Transfer Equipment," SET Portfolio: Process Systems Design,
]
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4/Session03.html.
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[41 M. Hindelang, J. Palazzolo and M. Robertson, "Condensers," Encyclopedia of CHemical

]
Engineering
Equipment:
University
of
Michigan,
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ml. [Accessed 25 March 2015].
[42 R. K. Sinnott, Chemical Engineering Design, Elsevier, 2005.
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]
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]
[45 "DESIGN PROJECTS," Benjamin M. Statler College of Engineering and Mineral
]
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[Accessed 10 May 2015].
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247
A p p e n d i x 1 Ac r y l i c Ac i d M a t e r i a l S a f e t y D a t a S h e e t
Appendix 1
Acrylic Acid Material Safety Data Sheet
248
249
250
251
252
253
254
Ap p e n d i x 2 In c o mb us tib le Ma te r ia ls
Appendix 2
Incombustible Materials
255
Ap p e n d i x 2 In c o mb us tib le Ma te r ia ls
Almost any contamination can potentially destabilize the monomer and should be avoided. The
following is a partial list of chemicals which are considered to be incompatible with acrylic
acid. In most cases, these contaminants cause polymerization of the monomer.
peroxides or peroxy- in name
per in name, e.g. t-butylperacetate
peresters or peroxyesters
percarbonates or peroxycarbonates
hydroperoxide or hydroperoxy- in name
azo compounds
azides
ethers (if containing peroxide)
amines
conjugated polyunsaturated acids and esters
aldehydes and some ketones
reactive inorganic halides (e.g. thionyl chloride, sulfuryl chloride)
caustics (e.g., NaOH, KOH, Ca(OH)2)
strong mineral acids (e.g., nitric, sulfuric, hydrochloric acids)
oxidizing agents (e.g., chromic acid, permanganates, nitric acid)
mercaptans
carboxylic acid anhydrides (rendering MeHQ inefficient)
inert gases (<5% Vol.-% oxygen)
certain transition metal ions
256
Ap p e n d i x 3 P o l ym a th s O DE Co m p le te In p u t a n d O u tp u t
Appendix 3
Polymaths ODE Complete Input and Output
257
Complete Input
# Component Mass Balance
d(Fpy)/d(V) = rpy
Fpy(0) = 228.6
d(Fo2)/d(V) = ro2
Fo2(0) = 505.62
d(Faa)/d(V) = raa
Faa(0) = 0
d(Fw)/d(V) = rw
Fw(0) = 1831.68
d(Fco2)/d(V) = rco2
Fco2(0) = 0
d(Fac)/d(V) = rac
Fac(0) = 0
# END Component Mass Balance
# Temperature Change Inside Reactor
d(T)/d(V) = (r1py * dHrxn1 + r2py * dHrxn2 + r3py * dHrxn3 - Ua * (T - Ta)) / sigma
T(0) = 464.15
Ua = 277533.5
sigma = Fpy * Cppy + Fo2 * Cpo2 + Faa * Cpaa + Fw * Cpw + Fco2 * Cpco2 + Fac * Cpac + Fi * Cpi
Cppy = 5.8139 + 0.2254 * Tout - 0.0001 * Tout ^ (2) + 2 / 100000000 * Tout ^ (3)
Cpo2 = 1E-09 * Tout ^ (3) - 7E-06 * Tout ^ (2) + 0.0157 * Tout + 25.01
Cpi = -0.0000000008 * Tout ^ (3) + 1E-06 * Tout ^ (2) + 0.0047 * Tout + 27.199
Cpaa = 2E-08 * Tout ^ (3) - 0.0001 * Tout ^ (2) + 0.2333 * Tout + 20.485
Cpw = -0.000000002 * Tout ^ (3) + 6E-06 * Tout ^ (2) + 0.0065 * Tout + 30.907
Cpco2 = 4E-09 * Tout ^ (3) - 2E-05 * Tout ^ (2) + 0.0487 * Tout + 25.473
Cpac = 2E-08 * Tout ^ (3) - 0.0001 * Tout ^ (2) + 0.2293 * Tout + 5.3717
dhfo2 = 0.0019 * Tout ^ (2) + 30.57 * Tout - 9657.8
dhfw = 0.0053 * Tout ^ (2) + 30.844 * Tout - 251867
dhfpy = 0.0257 * Tout ^ (2) + 86.912 * Tout - 13244
dhfaa = 0.0214 * Tout ^ (2) + 106.92 * Tout - 376673
dhfac = 0.0211 * Tout ^ (2) + 90.969 * Tout - 467614
dhfco2 = 0.0049 * Tout ^ (2) + 43.167 * Tout - 407917
dHrxn1 = dhfw + dhfaa - dhfpy - 1.5 * dhfo2
dHrxn2 = dhfw + dhfco2 + dhfac - dhfpy - 2.5 * dhfo2
dHrxn3 = 3 * dhfw + 3 * dhfco2 - dhfpy - 4.5 * dhfo2
# END Temperature Change Inside Reactor
# Ambient Temperature Change
d(Ta)/d(V) = Ua * (T - Ta) / mc / Cpc
Ta(0) = 473.15
Cpc = 1.56 # kj/kg/k
mc = 1926000 # CALCULATE IT in kg/h
# END Ambient Temperature Change
V(0) = 0
V(f) = 2.56
# Net Rate Laws
r1py = -k1 * exp(-E1 / R / Tout) * Ppy * Po2
Ppy = Fpy / FT * P0
Po2 = Fo2 / FT * P0
rpy = r1py + r2py + r3py
258
k1 = 159000
k3 = 181000000
k2 = 883000
E1 = 15000
E3 = 25000
E2 = 20000
R = 1.987
ro2 = 3 / 2 * r1py + 5 / 2 * r2py + 9 / 2 * r3py
raa = -r1py
rw = -r1py - r2py - 3 * r3py
rco2 = -r2py - 3 * r3py
rac = -r2py
# END Net Rate Laws
# Volumetric Flow Rate
FT0 = Fpy0 + Fo20 + Faa0 + Fw0 + Fco20 + Fac0 + Fi
Fpy0 = 228.6
Fo20 = 505.62
Faa0 = 0
Fw0 = 1831.68
Fco20 = 0
Fac0 = 0
Fi = 1902.06
FT = Fpy + Fo2 + Faa + Fw + Fco2 + Fac + Fi
FTh = Fpy + Fo2 + Faa + Fw + Fco2 + Fac
P0 = 430
T0 = 464.15
Tout = 583.15
# END Volumetric Flow Rate
Complete Output
Calculated values of DEQ variables
Variable Initial value Minimal value Maximal value Final value
1 V
2.56
2.56
2 Fpy
228.6
26.50778
228.6
26.50778
3 Fo2
505.62
94.24391
505.62
94.24391
4 Faa
158.1857
158.1857
5 Fw
1831.68
1831.68
2098.103
2098.103
6 Fco2
108.2378
108.2378
7 Fac
11.74093
11.74093
8 T
464.15
464.15
860.4126
588.1454
9 Ta
473.15
473.15
522.801
522.801
10 Ua
2.775E+05
2.775E+05
2.775E+05
2.775E+05
11 Fi
1902.06
1902.06
1902.06
1902.06
12 Tout
583.15
583.15
583.15
583.15
13 Cppy
107.2157
107.2157
107.2157
107.2157
14 Cpo2
31.98332
31.98332
31.98332
31.98332
15 Cpi
30.12122
30.12122
30.12122
30.12122
16 Cpaa
126.4937
126.4937
126.4937
126.4937
17 Cpw
36.34124
36.34124
36.34124
36.34124
259
18 Cpco2
47.86436
47.86436
47.86436
47.86436
19 Cpac
109.0478
109.0478
109.0478
109.0478
20 dhfo2
8815.217
8815.217
8815.217
8815.217
21 dhfw
-2.321E+05
-2.321E+05
-2.321E+05
-2.321E+05
22 dhfpy
4.618E+04
4.618E+04
4.618E+04
4.618E+04
23 dhfaa
-3.07E+05
-3.07E+05
-3.07E+05
-3.07E+05
24 dhfac
-4.074E+05
-4.074E+05
-4.074E+05
-4.074E+05
25 dHrxn1
-5.985E+05
-5.985E+05
-5.985E+05
-5.985E+05
26 dhfco2
-3.811E+05
-3.811E+05
-3.811E+05
-3.811E+05
27 dHrxn2
-1.089E+06
-1.089E+06
-1.089E+06
-1.089E+06
28 Cpc
1.56
1.56
1.56
1.56
29 mc
1.926E+06
1.926E+06
1.926E+06
1.926E+06
30 P0
430.
430.
430.
430.
31 sigma
1.645E+05
1.645E+05
1.659E+05
1.659E+05
32 dHrxn3
-1.925E+06
-1.925E+06
-1.925E+06
-1.925E+06
33 FT
4467.96
4399.08
4467.96
4399.08
34 Ppy
22.00064
2.591075
22.00064
2.591075
35 Po2
48.66127
9.212128
48.66127
9.212128
36 k1
1.59E+05
1.59E+05
1.59E+05
1.59E+05
37 k3
1.81E+08
1.81E+08
1.81E+08
1.81E+08
38 k2
8.83E+05
8.83E+05
8.83E+05
8.83E+05
39 E1
1.5E+04
1.5E+04
1.5E+04
1.5E+04
40 E3
2.5E+04
2.5E+04
2.5E+04
2.5E+04
41 E2
2.0E+04
2.0E+04
2.0E+04
2.0E+04
42 R
1.987
1.987
1.987
1.987
43 r1py
-406.3785
-406.3785
-9.060495
-9.060495
44 raa
406.3785
9.060495
406.3785
9.060495
45 r2py
-30.1624
-30.1624
-0.672492
-0.672492
46 r3py
-82.63336
-82.63336
-1.842369
-1.842369
47 rac
30.1624
0.672492
30.1624
0.672492
48 rpy
-519.1743
-519.1743
-11.57536
-11.57536
49 Fpy0
228.6
228.6
228.6
228.6
50 Fo20
505.62
505.62
505.62
505.62
51 Faa0
52 Fw0
1831.68
1831.68
1831.68
1831.68
53 Fco20
54 Fac0
55 FT0
4467.96
4467.96
4467.96
4467.96
56 ro2
-1056.824
-1056.824
-23.56263
-23.56263
57 FTh
2565.9
2497.02
2565.9
2497.02
58 rw
684.441
15.26009
684.441
15.26009
59 T0
464.15
464.15
464.15
464.15
60 rco2
278.0625
6.199598
278.0625
6.199598
260
Differential equations
1 d(Fpy)/d(V) = rpy
2 d(Fo2)/d(V) = ro2
3 d(Faa)/d(V) = raa
4 d(Fw)/d(V) = rw
5 d(Fco2)/d(V) = rco2
6 d(Fac)/d(V) = rac
7 d(T)/d(V) = (r1py * dHrxn1 + r2py * dHrxn2 + r3py * dHrxn3 - Ua * (T - Ta)) / sigma
8 d(Ta)/d(V) = Ua * (T - Ta) / mc / Cpc
Explicit equations
1 Ua = 277533.5
2 Fi = 1902.06
3 Tout = 583.15
4 Cppy = 5.8139 + 0.2254 * Tout - 0.0001 * Tout ^ (2) + 2 / 100000000 * Tout ^ (3)
5 Cpo2 = 1E-09 * Tout ^ (3) - 7E-06 * Tout ^ (2) + 0.0157 * Tout + 25.01
6 Cpi = -0.0000000008 * Tout ^ (3) + 1E-06 * Tout ^ (2) + 0.0047 * Tout + 27.199
7 Cpaa = 2E-08 * Tout ^ (3) - 0.0001 * Tout ^ (2) + 0.2333 * Tout + 20.485
8 Cpw = -0.000000002 * Tout ^ (3) + 6E-06 * Tout ^ (2) + 0.0065 * Tout + 30.907
9 Cpco2 = 4E-09 * Tout ^ (3) - 2E-05 * Tout ^ (2) + 0.0487 * Tout + 25.473
10 Cpac = 2E-08 * Tout ^ (3) - 0.0001 * Tout ^ (2) + 0.2293 * Tout + 5.3717
11 dhfo2 = 0.0019 * Tout ^ (2) + 30.57 * Tout - 9657.8
12 dhfw = 0.0053 * Tout ^ (2) + 30.844 * Tout - 251867
13 dhfpy = 0.0257 * Tout ^ (2) + 86.912 * Tout - 13244
14 dhfaa = 0.0214 * Tout ^ (2) + 106.92 * Tout - 376673
15 dhfac = 0.0211 * Tout ^ (2) + 90.969 * Tout - 467614
16 dHrxn1 = dhfw + dhfaa - dhfpy - 1.5 * dhfo2
17 dhfco2 = 0.0049 * Tout ^ (2) + 43.167 * Tout - 407917
18 dHrxn2 = dhfw + dhfco2 + dhfac - dhfpy - 2.5 * dhfo2
19 Cpc = 1.56
kj/kg/k
20 mc = 1926000
CALCULATE IT in kg/h
21 P0 = 430
22
sigma = Fpy * Cppy + Fo2 * Cpo2 + Faa * Cpaa + Fw * Cpw + Fco2 * Cpco2 + Fac * Cpac + Fi
* Cpi
23 dHrxn3 = 3 * dhfw + 3 * dhfco2 - dhfpy - 4.5 * dhfo2

24 FT = Fpy + Fo2 + Faa + Fw + Fco2 + Fac + Fi
25 Ppy = Fpy / FT * P0
26 Po2 = Fo2 / FT * P0
27 k1 = 159000
28 k3 = 181000000
29 k2 = 883000
30 E1 = 15000
261
31 E3 = 25000
32 E2 = 20000
33 R = 1.987
34 r1py = -k1 * exp(-E1 / R / Tout) * Ppy * Po2
35 raa = -r1py
38 rac = -r2py
39 rpy = r1py + r2py + r3py
40 Fpy0 = 228.6
41 Fo20 = 505.62
42 Faa0 = 0
43 Fw0 = 1831.68
44 Fco20 = 0
45 Fac0 = 0
46 FT0 = Fpy0 + Fo20 + Faa0 + Fw0 + Fco20 + Fac0 + Fi
47 ro2 = 3 / 2 * r1py + 5 / 2 * r2py + 9 / 2 * r3py
48 FTh = Fpy + Fo2 + Faa + Fw + Fco2 + Fac
49 rw = -r1py - r2py - 3 * r3py
50 T0 = 464.15
51 rco2 = -r2py - 3 * r3py
General
Total number of equations
Number of differential equations
Number of explicit equations
Elapsed time
Solution method
Step size guess. h
Truncation error tolerance. eps
59
8
51
1.157 sec
RKF_45
0.000001
0.000001
262
At ta c hme nts
Commented [HA9]:
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PROJECT Acrylic Acid

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King Saud University

ChE 422 Selected Topics in Chemical Engineering

Production of Acrylic Acid from Propylene

Perform extensive literature survey regarding the already-existing processes

Make modifications to the selected production process (if necessary)

Perform a HAZOP study

Carry out complete design calculations of major process equipment

Perform control loops on equipment units

Carry out plant location study

Carry out plant layout study

BRIEF HISTORY ................................................................................................................................. 2

USES AND APPLICATIONS .................................................................................................................. 3

PHYSICAL AND CHEMICAL PROPERTIES OF ACRYLIC ACID ................................................................... 4

PHYSICAL PROPERTIES ............................................................................................................................... 4

CHEMICAL AND THERMODYNAMIC PROPERTIES .............................................................................................. 5

SAFETY AND TOXICOLOGICAL PROPERTIES ...................................................................................................... 6

MARKET ANALYSIS ........................................................................................................................... 7

WORLDWIDE PRODUCTION OF ACRYLIC ACID ................................................................................................. 8

WORLDWIDE CONSUMPTION OF ACRYLIC ACID .............................................................................................. 9

PRICES OF ACRYLIC ACID AND ITS RAW MATERIALS ....................................................................................... 10

PRODUCTION OF ACRYLIC ACID FROM PROPYLENE .......................................................................... 11

PRODUCTION OF ACRYLIC ACID FROM PROPANE ............................................................................. 12

PRODUCTION OF ACRYLIC ACID FROM ACETYLENE ........................................................................... 13

PROCESS SELECTION ....................................................................................................................... 14

INSTABILITY OF ACRYLIC ACID ......................................................................................................... 19

HEALTH AND SAFETY FACTORS ........................................................................................................ 20

INDUSTRIAL HYGIENE .............................................................................................................................. 20

MEDICAL MANAGEMENT ......................................................................................................................... 20

FIRST AID .............................................................................................................................................. 20

PERSONAL PROTECTIVE EQUIPMENT ............................................................................................... 21

STORAGE OF ACRYLIC ACID ............................................................................................................. 22

TRANSPORT AND LOADING/UPLOADING ......................................................................................... 22

ENVIRONMENTAL CONSIDERATIONS ............................................................................................... 23

WASTE DISPOSAL ................................................................................................................................... 23

PRODUCTION OF ACRYLIC ACID BY PROPYLENE................................................................................ 24

MAXIMUM ALLOWABLE EXPOSURE LIMITS .................................................................................................. 24

TOXICOLOGY / HEALTH EFFECTS / HANDLING / PERSONAL PROTECTION ............................................................ 25

PREVIOUS INCIDENTS INVOLVING ACRYLIC ACID PRODUCTION ........................................................ 30

NIPPON SHOKUBAI HIMEJI PLANT INCIDENT ................................................................................................ 30

YOKOHAMA CHEMICAL FACTORY ............................................................................................................... 32

GUIDE WORDS AND PARAMETERS .................................................................................................. 35

STUDY NODES ................................................................................................................................ 35

BACKGROUND OF HEAT EXCHANGERS ............................................................................................. 64

FLOW ARRANGEMENT ............................................................................................................................. 64

TYPES OF HEAT EXCHANGERS .................................................................................................................... 64

Shell and Tube Heat Exchanger ................................................................................................ 64

Plate Heat Exchanger ............................................................................................................... 65

Plate and Shell Heat Exchanger ............................................................................................... 65

Double Pipe Heat Exchanger .................................................................................................... 66

Fluid Heat Exchanger ............................................................................................................... 66

Waste Recovery Heat Exchanger ............................................................................................. 66

CLASSIFICATION ACCORDING TO PROCESS FUNCTION..................................................................................... 66

Liquid to Vapor Phase Change Exchangers (Reboilers and Vaporizers) ................................... 68

HEAT EXCHANGER DESIGN EQUATIONS ....................................................................................................... 70

Overall Coefficient .................................................................................................................... 74

Pressure Drop ........................................................................................................................... 74

HORIZONTAL CONDENSER DESIGN EQUATIONS............................................................................................. 76

Overall Coefficient .................................................................................................................... 77

Pressure Drop ........................................................................................................................... 77

THERMOSYPHON REBOILER DESIGN EQUATIONS ........................................................................................... 78