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265 MTPD Production of
Purified Terephthalic Acid

by Amoco Process
DEPARTMENT OF CHEMICAL ENGINEERING
MUHAMMAD NAWAZ SHARIF UNIVERSITY OF

ENGINEERING AND TECHNOLOGY, MULTAN
265 MTPD Production of Purified Terephthalic
Acid by Amoco Process

MUHAMMAD NAWAZ SHARIF UNIVERSITY OF ENGINEERING AND
TECHNOLOGY, MULTAN
PROJECT ADVISOR
Dr. Waqas Aleem
PROJECT GROUP MEMBERS
Akasha Noor 2015-CH-708
Muhammad Bilal 2015-CH-709
Muhammad Ali 2015-CH-717
Rashail Ashas 2015-CH-718
SESSION
2015 - 2019

TECHNOLOGY, MULTAN
This Project Report is submitted to the Department of Chemical

Engineering, Muhammad Nawaz Sharif University of Engineering
and Technology, Multan for the fulfillment of requirements for the
Approved On
Thesis Supervisor
Name Dr. Waqas Aleem
Signature
External Examiner
Name
Signature
Head of Department/Project Incharge
Name Dr. Asim Umer
Signature

TECHNOLOGY, MULTAN
Acknowledgment
All praise to Almighty ALLAH, who provided us with the strength to accomplish this project
report. All respects are for His HOLY PROPHET (Peace Be Upon Him), whose teachings are
true source of knowledge & guidance for whole mankind.
Before anybody else, we would like to thank our Parents who have always been a source of
moral support, driving force behind whatever we do. We are indebted to our project advisor
Dr. Waqas Aleem for his worthy discussions, encouragement, technical discussions, inspiring
guidance, remarkable suggestions, keen interest, constructive criticism & friendly discussions
that enabled us to complete this report.
We are thankful to the Head of Department and Project In-charge Dr. Asim Umer for
providing facilities and guidance. We are also thankful to all of our teachers for their keen and
sincere efforts and suggestions that proved to be very helpful in achieving our goal.

TECHNOLOGY, MULTAN
Abstract
Terephthalic acid (TPA) is the building block of plastic production industries. It is a very
important for the production of Poly-Ethylene Terephthalate. TPA is produced by the high
pressure, high temperature catalytic oxidation of para xylene. Pakistan is currently in a lot of
need of TPA as the demand of plastic industry for TPA is much greater. The objective of this
project report is to deal with design calculations of 265 metric tons per day production rate of
purified TPA along with their manufacturing aspects such as Material and Energy Balance,
Equipment Design, Instrumentation, cost Estimation, HAZOP study and Environmental
Aspects. Keeping these points in Mind. This report is divided in to different sections;
introduction of TPA, literature review, process description, material and energy balance,
equipment design, cost Estimation, HAZOP study, instrumentation and environmental aspects
of Terephthalic Acid Production Plant.
Our project ensures the purity of final product to be 99.99%. The selection of this project was
based on the increasing need of TPA in the Plastic industry of Pakistan. Our project employs
The only
sole producer of TPA in bulk in Pa t is
implemented, our plant will be able to complete the remaining need of TPA for Pakistani plastic
industry.

TECHNOLOGY, MULTAN
Undertaking
I certify that thesis work titled 265 MTPD Production of Purified Terephthalic Acid by Amoco
Process is our own work. The work has not been presented elsewhere for assessment. Where
material has been used from other sources it has been properly acknowledged / referred.
Name Registration No. Signature
Akasha Noor 2015-CH-708
Muhammad Bilal 2015-CH-709
Muhammad Ali 2015-CH-717
Rashail Ashas 2015-CH-718

TECHNOLOGY, MULTAN
teachers whose tremendous support and cooperation led
us to thi
265 MTPD Production of Purified Terephthalic Acid by Amoco Process
List of Figures
Figure 1- 1 Purified Terephthalic acid/PX price trend, 2017[2] _______________________ 28
Figure 1- 2 PTA capacity- pacific Asian 2016 ____________________________________ 29
Figure 1- 3 Global productions 2014 ___________________________________________ 29
Figure 1- 4 Global exports 2016 _______________________________________________ 30
Figure 1- 5 Global consumption 2015 __________________________________________ 30
Figure 2- 1 Importance of PET & TPA 35
Figure 2- 2 Reaction Scheme _________________________________________________ 37
Figure 2- 3 Hydrolysis Reaction _______________________________________________ 40
Figure 2- 4 Global Production of PET __________________________________________ 43
Figure 2- 5 Growth rate of PET per year ________________________________________ 44
Figure 2- 6 Catalytic Isomerization of dipotassium o-phthalate_______________________ 47
Figure 2- 7 Two-step conversion to TPA reaction from dipotassium p-phthalate _________ 48
Figure 2- 8 Ammoxidation of p-xylene _________________________________________ 49
Figure 2- 9 Acid oxidation of p-xylene__________________________________________ 51
Figure 2- 10 Process Flow Diagram ___________________________________________ 54
Figure 2- 11 TPA Demand Chart ______________________________________________ 56
Figure 3- 1 FMT material balance 58
Figure 3- 2 CSTR Reactor 1 material balance ____________________________________ 59
Figure 3- 3 Condenser 1 and Gas Liquid Separator material balance __________________ 60
Figure 3- 4 Crystallizer and De-Engaging Vessel material balance ____________________ 61
Figure 3- 5 Centrifuge 1 material balance _______________________________________ 63
Figure 3- 6 Dryer 1 material balance ___________________________________________ 64
Figure 3- 7 Re-Slurry Tank and Reactor 2 material balance _________________________ 65

MUHAMMAD NAWAZ SHARIF UNIVERSITY OF ENGINEERING AND TECHNOLOGY, MULTAN
Figure 3- 8 Crystallizer 2 and de-engaging tank material balance _____________________ 66
Figure 3- 9 Centrifuge 2 material balance _______________________________________ 67
Figure 3- 10 Dryer 2 material balance __________________________________________ 68
Figure 3- 11 Pre-Heater heat balance ___________________________________________ 69
Figure 3- 12 Compressor heat balance __________________________________________ 70
Figure 3- 13 Cooler heat balance ______________________________________________ 70
Figure 3- 14 Reactor heat balance _____________________________________________ 71
Figure 3- 15 condenser heat balance ____________________________________________ 72
Figure 3- 16 Crystallizer heat balance __________________________________________ 72
Figure 3- 17 Condenser heat balance ___________________________________________ 74
Figure 3- 18 Dryer heat balance _______________________________________________ 74
Figure 3- 19 Pre-Heater 2 heat balance__________________________________________ 76
Figure 3- 20 Compressor 2 heat balance_________________________________________ 76
Figure 3- 21 Reactor 2 heat balance ____________________________________________ 77
Figure 3- 22 Crystallizer 2 heat balance _________________________________________ 78
Figure 3- 23 Condenser 2 heat balance __________________________________________ 79
Figure 3- 24 Dryer 2 heat balance______________________________________________ 79
Figure 4- 1 Classification of Reactors 90
Figure 4- 2 Classification of Reactors __________________________________________ 91
Figure 4- 3 Lumped kinetic scheme for the oxidation of p-xylene to terephthalic acid _____ 94
Figure 4- 4 Pictorial View of Pitched 6-Blade Turbine _____________________________ 99
Figure 4- 5 Temperature Pattern in continuous counteracting adiabatic Dryers _________ 111
Figure 4- 6 Solubility trend of TPA in Water ____________________________________ 123
Figure 6- 1 Component Selection 143
Figure 6- 2 Fluid Package Selection ___________________________________________ 143

Figure 6- 3 Worksheet _____________________________________________________ 144
Figure 7- 1 Feedback Control loop on Shell and tube Heat Exchanger 147
Figure 8- 1 HAZOP Method flow Diagram 151
List of Charts
Chart 9- 1 Shell Side Heat transfer coefficient curve ______________________________ 164
Chart 9- 2 Viscosity of Gases ________________________________________________ 165
Chart 9- 3 Viscosity of Liquids_______________________________________________ 166
Chart 9- 4 Humidity Charts__________________________________________________ 167
Chart 9- 5 Enthalpy Entropy Diagram _________________________________________ 168

List of Tables
Table 1- 1 Physical properties_________________________________________________ 27
Table 1- 2 Thermodynamics properties ________________________________________ 27
Table 2- 1 Properties of TPA 36
Table 2- 2 Process comparison ________________________________________________ 52
Table 3- 1 FMT Material Balance 58
Table 3- 2 CSTR Reactor 1 material balance _____________________________________ 59
Table 3- 3 CSTR Reactor 1 material balance _____________________________________ 60
Table 3- 4 Condenser 1 material balance ________________________________________ 60
Table 3- 5 Gas Separator material balance _______________________________________ 61
Table 3- 6 Crystallizer 1 material balance _______________________________________ 62
Table 3- 7 Crystallizer 1 material balance _______________________________________ 62
Table 3- 8 Partial Condenser 2 material balance __________________________________ 62
Table 3- 9 De-Engaging Vessel material balance __________________________________ 63
Table 3- 10 Centrifuge 1 material balance _______________________________________ 64
Table 3- 11 Dryer 1 material balance ___________________________________________ 64
Table 3- 13 Re-Slurry Rank material balance_____________________________________ 65
Table 3- 14 Reactor 2 material balance _________________________________________ 66
Table 3- 15 Reactor 2 material balance _________________________________________ 66
Table 3- 16 Crystallizer 2 material balance ______________________________________ 67
Table 3- 17 Partial Condenser material balance ___________________________________ 67
Table 3- 18 De-Engaging Vessel 2 material balance _______________________________ 67

Table 3- 19 Centrifuge 2 material balance _______________________________________ 68
Table 3- 21 Pre-Heater heat balance ____________________________________________ 69
Table 3- 22 pre-heater heat balance ____________________________________________ 69
Table 3- 23 Compressor heat balance ___________________________________________ 70
Table 3- 24 Compressor heat balance ___________________________________________ 70
Table 3- 25 Reactor heat balance ______________________________________________ 71
Table 3- 28 Crystallizer heat balance ___________________________________________ 73
Table 3- 31 Condenser heat balance ____________________________________________ 74
Table 3- 32 Dryer energy balance ______________________________________________ 75
Table 3- 33 Pre-Heater 2 heat balance __________________________________________ 76
Table 3- 34 Compressor 2 heat balance _________________________________________ 76
Table 3- 35 Reactor 2 heat balance _____________________________________________ 77
Table 3- 36 Reactor 2 heat balance _____________________________________________ 77
Table 3- 37 Crystallizer 2 heat balance__________________________________________ 78
Table 3- 40 Condenser 2 heat balance __________________________________________ 79
Table 3- 41 Dryer 2 heat balance ______________________________________________ 80
Table 3- 42 Dryer 2 heat balance ______________________________________________ 80

Table 4- 1 Heat exchanger comparison 82
Table 4- 2 Selection Parameters _______________________________________________ 83
Table 4- 3 Heat Exchanger Configuration _______________________________________ 83
Table 4- 4 Heat Exchanger Specification Sheet ___________________________________ 88
Table 4- 5 Choice of Agitator _________________________________________________ 98
Table 4- 6 Specification Sheet of Agitator ______________________________________ 101
Table 4- 7 Specification Sheet of Agitator ______________________________________ 105
Table 4- 8 Inlet and Outlet Temperature of Dryer ________________________________ 111
Table 4- 9 Dryer Specification Sheet __________________________________________ 118
Table 4- 10 Crystallizer comparison ___________________________________________ 121
Table 4- 11 Properties of magma _____________________________________________ 123
Table 4- 12 Temperature differences __________________________________________ 126
Table 4- 13 Crystallizer Specification Sheet ____________________________________ 132
Table 5- 1 Equipment Cost 137
Table 5- 2 Direct Cost ______________________________________________________ 138
Table 5- 3 Indirect Cost ____________________________________________________ 138
Table 5- 4 Raw Material Cost ________________________________________________ 139
Table 8- 1 HAZOP Guide Words and Meanings 152
Table 8- 2 HAZOP Guide Words and Meanings _________________________________ 153
Table 8- 3 Flammability Limits ______________________________________________ 155

Table of Contents
1 INTRODUCTION _______________________________________________________ 26
1-1 Project Overview _______________________________________________________ 26
1-2 Terephthalic acid _______________________________________________________ 26
1-3 Industrial application ____________________________________________________ 27
1-4 Global purified Terephthalic acid market _____________________________________ 28
1-5 Feedstock _____________________________________________________________ 31
1-5-1 Para xylene ________________________________________________________ 31
1-5-2 Uses ______________________________________________________________ 31
1-6 Problem Statement ______________________________________________________ 32
1-7 Objectives _____________________________________________________________ 32
2 LITERATURE REVIEW & PROCESS DESCRIPTION _______________________ 34
2-1 Importance of PET and TPA ______________________________________________ 35
2-2 Properties of TPA _______________________________________________________ 35
2-3 TPA Manufacturing Technologies __________________________________________ 36
2-4 Direct oxidation of p-xylene _______________________________________________ 36
2-5 Process Description _____________________________________________________ 37
2-5-1 Toray process _______________________________________________________ 37
2-5-2 Mitsubishi Kasei process ______________________________________________ 38
2-5-3 Eastman Process ____________________________________________________ 38
2-5-4 Hydrolysis of DMT __________________________________________________ 39
2-5-5 Amoco Process _____________________________________________________ 40
2-6 Steps Involved in Amoco Process __________________________________________ 42
2-6-1 Process feedstock ____________________________________________________ 42

2-6-2 Oxidation __________________________________________________________ 42
2-6-3 Crystallization, filtration and drying _____________________________________ 42
2-6-4 Purification (hydrogenation) ___________________________________________ 42
2-7 Market of PET _________________________________________________________ 43
2-8 Global Production of PET ________________________________________________ 43
2-9 Worldwide Major Producers ______________________________________________ 43
2-10 Global market forecast for PET ___________________________________________ 44
2-11 Raw Materials Worldwide _______________________________________________ 44
2-11-1 P-xylene __________________________________________________________ 44
2-11-2 Acetic acid ________________________________________________________ 45
2-12 Kinetic Study for Production of TPA _______________________________________ 45
2-13 Uses of Purified Terephthalic Acid (PTA) ___________________________________ 45
PROCESS DESCRIPTION AND SELECTION ________________________________ 47
2-14 Production processes ___________________________________________________ 47
2-15 Henkel Process (Rearrangement of Benzoic acid and Phthalic anhydride) __________ 47
2-16 Ammoxidation of p-xylene (Lummus process) _______________________________ 48
2-17 Amoco Process ________________________________________________________ 49
2-18 Du Pont process _______________________________________________________ 51
2-19 Process selection _______________________________________________________ 52
2-20 Process Description ____________________________________________________ 53
2-20-1 Crude TPA Section _________________________________________________ 53
2-20-2 Purified TPA section ________________________________________________ 53
2-20-3 Process Flow diagram _______________________________________________ 54
2-21 Plant capacity _________________________________________________________ 55

3 MATERIAL & ENERGY BALANCE_______________________________________ 58
3-1 Feed Mixing Tank Material Balance ________________________________________ 58
3-1-1 Assumptions _______________________________________________________ 58
3-1-2 General Material Balance Equation ______________________________________ 58
3-2 CSTR Reactor 1 Material Balance __________________________________________ 59
3-2-1 Assumptions _______________________________________________________ 59
3-2-2 General Material Balance Equation ______________________________________ 59
3-3 Condenser and Gas Liquid separator Material Balance __________________________ 60
3-4 Crystallizer and De-Engaging Vessel material balance __________________________ 61
3-5 Centrifuge 1 material balance ______________________________________________ 63
3-6 Dryer 1 material balance__________________________________________________ 64
3-7 Re-Slurry Tank and Reactor 2 Material balance _______________________________ 65
3-8 Crystallizer and De-Engaging Tank material balance ___________________________ 66
3-9 Centrifuge 2 material balance ______________________________________________ 67
3-10 Dryer 2 material balance_________________________________________________ 68
ENERGY BALANCE ______________________________________________________ 69
3-11 Heat Balance on Pre-Heater H-101 ________________________________________ 69
3-12 Heat Balance on compressor CS-101 _______________________________________ 70
3-13 Heat Balance on Cooler CO-101 __________________________________________ 70
3-14 Heat Balance on Reactor R-101 ___________________________________________ 71
3-15 Heat Balance on Condenser C-101 _________________________________________ 72
3-16 Heat Balance on Crystallizer CR-101: ______________________________________ 72
3-17 Heat Balance on Condenser C-10 __________________________________________ 74
3-18 Heat Balance on Dryer DR-101 ___________________________________________ 74

3-19 Heat Balance on Re-Slurry tank ___________________________________________ 75
3-20 Heat Balance on Pre-heater H-201 _________________________________________ 76
3-21 Heat Balance on compressor CS-201 _______________________________________ 76
3-22 Heat Balance on Reactor R-201 ___________________________________________ 77
3-23 Heat Balance on Crystallizer CR-201 ______________________________________ 78
3-24 Heat Balance on Condenser C-201 _________________________________________ 79
3-25 Heat Balance on Dryer D-201 ____________________________________________ 79
4 EQUIPMENT DESIGN___________________________________________________ 82
4-1 DESIGN OF SHELL AND TUBE PRE-HEATER: __________________________ 82
4-1-1 Selection Criteria ______________________________________________________ 82
4-1-2 Selection parameter of our design _________________________________________ 83
4-1-3 Shell and tube heat exchanger (Configuration Selection) _______________________ 83
4-1-4 Design Steps of Heat Exchanger __________________________________________ 83
4-1-4 Calculation of heat exchanger ____________________________________________ 84
4-1-4-1 Heat duty ________________________________________________________ 84
4-1-4-2 Mass flow rate of steam _____________________________________________ 84
4-1-4-3 Properties of hot steam ______________________________________________ 84
4-1-4-4 Log mean temperature difference _____________________________________ 84
4-1-4-5 Assumption_______________________________________________________ 85
4-1-4-6 Provisional area ___________________________________________________ 85
4-1-4-7 Tube configuration _________________________________________________ 85
4-1-4-8 Bundle and shell diameter ___________________________________________ 85
4-1-4-9 Tube side coefficient (Hot fluid) ______________________________________ 86
4-1-4-10 Overall coefficient ________________________________________________ 87

4-1-4-11 Shell side coefficient ______________________________________________ 87
4-1-4-12 Pressure drop calculation ___________________________________________ 87
4-1-5 Specification sheet_____________________________________________________ 88
4-2 REACTOR DESIGN ___________________________________________________ 89
4-2-1 Reactor System _______________________________________________________ 89
4-2-2 Overall Reaction ______________________________________________________ 89
4-2-3 Reaction Operating Conditions ___________________________________________ 89
4-2-4 Choice of Reactor _____________________________________________________ 90
4-2-5 Pictorial View of the contacting Pattern of Liquid-Gas Reactions ________________ 91
4-2-6 Choice of Reactor _____________________________________________________ 92
4-2-7 Designing of Continuous Stirred Tank Reactor (CSTR) _______________________ 93
4-2-7-1 Mathematical Calculations ___________________________________________ 93
4-2-7-1 Values of rate constant k (min-1) ______________________________________ 94
4-2-7-2 Calculation of CAo _________________________________________________ 94
4-2-7-3 Rate Equation _____________________________________________________ 94
4-2-7-4 Design Equation ___________________________________________________ 94
4-2-7-5 Calculating Length and Diameter of the Reactor __________________________ 95
4-2-7-6 Available Area ____________________________________________________ 95
4-2-7-7 Jacket Design _____________________________________________________ 95
4-2-7-8 Heat Calculations __________________________________________________ 95
4-2-7-9 Choice of Coolant__________________________________________________ 95
4-2-7-10 Mathematical Calculations __________________________________________ 96
4-2-7-11 Choice of Agitator ________________________________________________ 97
4-2-7-12 Specification Sheet for Agitator _____________________________________ 101

4-2-7-13 Mechanical Design of Reactor ______________________________________ 102
4-2-7-14 Specification Sheet for Continuous Stirred Tank Reactors ________________ 105
4-3 DESIGNING OF DRYER ______________________________________________ 106
4-3-1 Brief Introduction ____________________________________________________ 106
4-3-2 Classification of Dryers ________________________________________________ 106
4-3-3 Selection of dryer ____________________________________________________ 107
4-3-3-1 From Classification No. 1 __________________________________________ 107
4-3-3-2 From Classification No. 2 __________________________________________ 107
4-3-4 Indirect Heat Rotary Dryer _____________________________________________ 107
4-3-5 Design Considerations_________________________________________________ 108
4-3-6 Solid Feed Rate and Moisture Content ____________________________________ 108
4-3-7 Temperature Selection & Calculations ____________________________________ 109
4-3-8 Humidity of Inlet air (H1) ______________________________________________ 109
4-3-9 Outlet air temperature (Tb) _____________________________________________ 110
4-3-10 Temperature Pattern In dryers __________________________________________ 111
4-3-11 Temperatures _______________________________________________________ 111
4-3-12 Drum Diameter _____________________________________________________ 112
4-3-13 Calculation of heat load on dryer (qt) ____________________________________ 112
4-3-14 Calculation for air flow rate (mg) _______________________________________ 113
4-3-15 Air mass velocity (G) ________________________________________________ 113
4-3-16 Area of dryer (A) ____________________________________________________ 113
4-3-17 Drum Diameter _____________________________________________________ 113
4-3-18 Drum Length _______________________________________________________ 114
4-3-19 Calculation for Volumetric heat transfer coefficient (Ua) ____________________ 114

4-3-20 Calculate the volume of dryer (V)_______________________________________ 114
4-3-21 Calculation for log mean of drying gas wet bulb depression at inlet & exit end of dryer
( Tm) __________________________________________________________________ 114
4-3-22 Length of dryer _____________________________________________________ 115
4-3-23 L/D ratio __________________________________________________________ 115
4-3-24 Rotational Speed ____________________________________________________ 115
4-3-25 Lifting Flights ______________________________________________________ 115
4-3-26 Flights Heights _____________________________________________________ 115
4-3-27 Flights depth _______________________________________________________ 116
4-3-28 Shape of Flights _____________________________________________________ 116
4-3-29 Residence Time _____________________________________________________ 116
4-3-30 Outlet Humidity_____________________________________________________ 116
4-3-31 Specification Sheet __________________________________________________ 118
4-4 CRYSTALLIZER DESIGN ____________________________________________ 120
4-4-1 Selection of Crystallizer _______________________________________________ 120
4-4-2 Tank Crystallizer _____________________________________________________ 120
4-4-3 Scraped-Surface Cooled Crystallizer _____________________________________ 120
4-4-4 Forced Circulation Crystallizer __________________________________________ 120
4-4-5 Circulating Liquor Crystallizer __________________________________________ 121
4-4-6 Pre-Requisites _______________________________________________________ 121
4-4-7 Comparison & Selection of Crystallization ________________________________ 121
4-4-7-1 Advantages ______________________________________________________ 122
4-4-7-2 Disadvantage ____________________________________________________ 122
4-4-8 Design Calculations___________________________________________________ 122

4-4-8-1 Design Procedure _________________________________________________ 122
4-4-8-2 Properties _______________________________________________________ 123
4-4-8-3 Solubility _______________________________________________________ 123
4-4-8-4 Assumptions _____________________________________________________ 124
6-4-8-5 Heat transfer Calculations __________________________________________ 125
4-4-8-6 Evaporation rate __________________________________________________ 129
4-4-8-7 Maximum Vapor Velocity __________________________________________ 130
4-4-8-8 Yield of Crystallization ____________________________________________ 131
4-4-9 SPECIFICATION SHEET _____________________________________________ 132
5 COST ESTIMATION ___________________________________________________ 134
5-1 Cost Estimation of Reactor _______________________________________________ 134
5-2 Cost Estimation of Crystallizer____________________________________________ 134
5-3 Cost Estimation of Heat Exchanger ________________________________________ 135
5-4 Cost Estimation of Pump ________________________________________________ 136
5-5 Cost Estimation of Cooler _______________________________________________ 136
5-6 Cost Estimation of Dryer ________________________________________________ 137
5-7 Equipment Cost _______________________________________________________ 137
5-8 Working Capital Investment ______________________________________________ 138
5-9 Total product cost ______________________________________________________ 138
5-10 Raw material cost _____________________________________________________ 139
5-11 Gross earning/income __________________________________________________ 140
5-12 Rate of return ________________________________________________________ 140
5-13 Payback period _______________________________________________________ 140
6 PROCESS SIMULATION _______________________________________________ 142

6-1 Introduction to Process Simulation and Aspen HYSYS ________________________ 142
6-2 Simulation Procedure ___________________________________________________ 142
6-3 Simulation Results _____________________________________________________ 143
7 INSTRUMENTATION AND CONTROL __________________________________ 146
7-1 Control Loops _________________________________________________________ 146
7-2 Components of a control system __________________________________________ 146
7-2-1 Process ___________________________________________________________ 146
7-2-2 Measuring devices __________________________________________________ 146
7-2-3 Controller _________________________________________________________ 146
7-2-4 Final control element ________________________________________________ 146
7-3 Temperature Control and Measurement _____________________________________ 147
7-4 Control of Pre-Heater ___________________________________________________ 147
8 HAZOP STUDY & ENVIRONMENTAL IMPACT ASSESSMENT ____________ 149
8-1 Hazard and Operability Study (Hazop) _____________________________________ 149
8-2 Steps Conducted In Hazop Study __________________________________________ 149
8-3 Study ________________________________________________________________ 150
ENVIRONMENTAL IMPACT ASSESSMENT _______________________________ 154
8-4 Definition ____________________________________________________________ 154
8-5 Exposure _____________________________________________________________ 154
8-6 Flammability__________________________________________________________ 155
8-7 Water Hazards ________________________________________________________ 155
8-8 Treatment ____________________________________________________________ 156
8-8-1 Concentration______________________________________________________ 156
8-8-2 Digestion _________________________________________________________ 156

8-8-3 Conditioning ______________________________________________________ 156
8-8-4 Dewatering________________________________________________________ 156
8-8-5 Oxidation _________________________________________________________ 156
8-8-6 Ultimate Sludge Disposal ____________________________________________ 157
8-9 Human Exposure ______________________________________________________ 157
8-9-1 Consumer Exposure_________________________________________________ 157
8-9-2 Occupational Exposure ______________________________________________ 157
8-10 Environmental Precautions of Para Xylene _________________________________ 158
8-11 Accidental Release Measures for Acetic Acid _______________________________ 158
9 APPENDIX ____________________________________________________________ 159
REFERENCES __________________________________________________________ 169

CHAPTER 1
Introduction
PRODUCTION OF PURIFIED TPA CHAPTER 01
1 Introduction
1-1 Project Overview
The Group of a senior class of Chemical Engineering has been assign to design a Purified
Terephthalic Acid (TPA) plant using oxidation of para xylene as the raw material. The team
needs to incorporate safety aspects, site selection, conceptual design, material and energy
balance, heat integration and preliminary economic evaluation in the design of plant.
1-2 Terephthalic acid
Terephthalic acid is a benzenedi-carboxylic acid carrying carboxy groups at positions 1 and 4.

One of three possible isomers of benzenedi-carboxylic acid, the others being Phthalic and iso-
phthalic acids. It is a conjugate acid of terephthalate.
Terephthalic acid, a raw material for polyethylene terephthalate production, is one of the most
important chemicals in petrochemicals industry. Crude Terephthalic acid commonly produced
by homogeneous liquid phase of Para xylene oxidation, contains impurities such as 4-CBA
(carboxybenzaldehyde) and several colored poly aromatics that should be removed to obtain
purified Terephthalic acid.
Terephthalic acid is usually obtain by the catalytic oxidation of p-xylene in air, in the presence
of acetic acid as solvent. Once the synthesis is complete, the solvent is to be recycled and reused
back to the chemical reaction media.
Purified Terephthalic acid manufacturing process consists of two steps, namely, oxidation and
purification. During oxidation step, the p-xylene oxidation reaction takes place in the liquid
phase and is catalyzed by a Co-Mn-Br at the (150-
Terephthalic acid[1].
26
Table 1- 1 Physical properties[1]

Properties Unit Terephthalic acid
Molecular weight g/mole 166.13
Boiling point 214.32
Vapor pressure mmHg
Specific gravity 1.51
Solubility mg/l 15
Density g/cm3 1.51
Molecular formula C8H6O4
Color White
Table 1- 2 Thermodynamics properties[1]

Properties Unit Terephthalic acid
Specific heat Cal/goC 0.2873
Triple Point K 700
1-3 Industrial application
The aromatic ring of PTA imparts excellent hardness, corrosion and stain resistance to coatings
reins. Such other industrial application of PTA are given as[1]
Adhesives
Architectural coating
Automotive
Coil coating
Graphics arts
Intermediates
Paints & coatings
Protective coating
Water packing
Pharmaceutical industry
Polyester coating resins
27
1-4 Global purified Terephthalic acid market
The purified Terephthalic acid market is likely to observe a noticeable growth in the
approaching years owing to a high demand for polyester resin. Poly Ethylene Terephthalate
demand is also anticipated to have a positive impact on the purified Terephthalic acid market.
The rising per capita consumption and the growing disposable income in the developing
economics such as India and China along with a significant growth of the textile, coating and
packing industries in these region is predicted to fuel the demand for the purified Terephthalic
acid market.
Industries such as the beer industry and the household product containers industry are still
dominated by the glass industry, which is an unexplored market for purified Terephthalic acid
consumption, offering new opportunities for the growth of purified Terephthalic acid market[2].
Figure 1- 1 Purified Terephthalic acid/PX price trend, 2017[2]
The PTA price crossed the US$ 700/MT mark in November. The average price of PTA in
spot market was US$ 655/MT.
28
China South korea Taiwan India Pakistan
1%
10%
19%
48%
22%
Figure 1- 2 PTA capacity- pacific Asian 2016[1]
In 2016 the production capacity for PTA reached 80 million tons from 70 million tons in
2014
Asia Westren Europe China USA
13%
21%
55%
11%
Figure 1- 3 Global productions 2014[1]
29
Asia Westren Europe Japan Middle East
4%
6%
22%
68%
Figure 1- 4 Global exports 2016[1]
Asia pacific export PTA 62%, western Europe 20%, japan and middle east export PTA 5% &
4% respectively
China Westren Europe USA Canada
1%
4%
18%
77%
Figure 1- 5 Global consumption 2015[1]
30
1-5 Feedstock
Feedstock for the production of Purified TPA consist of oxidation of Para xylene[1]
1-5-1 Para xylene
Para xylene also known as px or p-xylene is an aromatic hydrocarbon compound, derived

particularly from benzene. Para xylene is a colorless, toxic, sweet smelling, and high flammable
chemical at room temperature. It is found naturally in petroleum and coal tar. Para xylene is an
isomer of xylene compound, derived from benzene. Some of the other isomers of xylene
include o-xylene and m-xylene. Para xylene finds its largest application in large-scale
manufacturing of Terephthalic acid for polyester[1].
1-5-2 Uses
Production of Terephthalic acid monomer

Good cleaning agent for silicon wafers, steel and to sterilize many substances
31
1-6 Problem Statement
Purified Terephthalic acid is a raw material, which is use in the production of high performance
multipurpose plastics like poly butylene terephthalate (PBT), polyethylene terephthalate
(PET). Purified Terephthalic acid is also use in automotive, intermediate and paint & coating
industry. The main feedstock for purified Terephthalic acid industry are Para xylene and fresh
air. However, due to its increasing cost of Para xylene. The team is assigned the task of
designing a purified Terephthalic acid production plant using a pre-specified composition of
Para-xylene as the raw material. Purified Terephthalic acid is produced by bromine promoted
catalytic oxidation of Para xylene and then is purified by the process of hydrogenation
(AMOCO PROCESS).
1-7 Objectives
The objective of this project is to develop a purified Terephthalic acid production plant. The
plant must be cost effective, considers all of the desired criteria in addition to dealing with
relevant issue. The team needs to recommend the best possible design, which will ultimately
convince panel of juries to verify the new plant. The objectives of this design project include
the following:
To integrate chemical engineering skills and knowledge in a detailed design of a

chemical plant.
To apply appropriate design codes in a detailed design work.
To present a piping and instrumentation diagram (P&ID) and control strategy packages.
To perform detailed economic evaluation of the proposed chemical plant.
To generate cost effective process options while maintaining operability, safety and
environment friendly of the design.
32
CHAPTER 2
Literature Review
&
Process Description
2 LITERATURE REVIEW & PROCESS DESCRIPTION

Polyethylene Terephthalate (PET) is a polymer that possesses great importance in the
contemporary world of plastics. Being a thermoplastic i.e. recyclable polymer made it the
number one choice for numerous applications, which satisfies the world need for a greener and
more ecological alternative to commonly used plastics such as polyethylene and others.
Nowadays, Two PET grades dominate the global market fiber-grade PET and bottle-grade
PET. They differ mainly in the product properties such as optical appearance and production
technologies where these properties can be controlled by molecular weight, intrinsic viscosity,
and additives specific to each process. Other uses include film production and specialty nylons.
Terephthalic acid is the main raw material in PET manufacturing industries [3].
During the period 1942-1944 Whinfield, Dickson and Hardy made Terephthalic Acid (TPA)
by dehydrogenating dipentene with sulfur to form P-cymene (P-isopropyl toluene), which they
oxidized in two stages, where in the first with dilute nitric acid ,and then with alkaline
permanganate. The first commercial route for forming the PET fiber was through oxidation of
p-xylene under pressure using dilute nitric acid. This method had some problems as the
product contained color, and color forming impurities that could not be removed. This required
the replacement of this method by another that gives better product purity; this is why the
method of esterification with methanol to form Dimethyl Terephthalate (DMT) was employed.
Later it was discovered that some DMT production routes are hazardous, so researches were
made to produce TPA from p-xylene directly via air oxidation. Another problem was found
then, which was the high oxidation resistance of the intermediate p-toluic acid. Using acetic
acid as a solvent and oxygen as an oxidant instead of air solved this problem
enabling the use of TPA in polymerization directly.
With the development of the process, the separation equipment also developed. This
development opened the way for the production of PET as a beverages container. Because the
bottle-grade PET needed higher molecular weight and intrinsic viscosity, the need for a more
purification of TPA was essential. Now the production of TPA with the needed purity is
applicable with considerable ease [3].
34
2-1 Importance of PET and TPA
The importance of PET comes from the fact that it is widely used in many products either alone
or as a co-monomer. Also the PET pre-polymerization intermediate (TPA) can be used to
produce other products. The following part shade light on the importance of PET and its
monomers, through stating the most important uses in which they are used [3].
Terephthalic Acid (TPA)
Monoethylene Glycol (MEG)
Polyethylene Terephthalate (PET)
Figure 2- 1 Importance of PET & TPA[3]
2-2 Properties of TPA
TPA properties, as a PET production intermediate, are shown in the table below mentioning
some physical and chemical properties.
35
Table 2- 1 Properties of TPA[4]

Properties of TPA
Appearance White crystals or powder
Molecular Weight g/mole 166
Melting point, °C 427 for sealed tube
Triple point, °C 427
Specific gravity at 25 °C 1.522
Specific heat, J/Kg K 1202
Sublimation point, °C 404
Heat of combustion at 25 °C, kJ/mole -3198
Heat of formation at 25°C, kJ/mole -816
Heat of sublimation, kJ/mole 142
Biodegradation Readily biodegradable
2-3 TPA Manufacturing Technologies
TPA can be manufactured from different raw materials and through several routes. Several
technologies have been developed to achieve the most economical way of production. The
following part explains different processes with flow sheets and technical description [3].
2-4 Direct oxidation of p-xylene
TPA is produced by oxidation of p-xylene. There are different technologies to produce TPA
according to oxidation process as follow:
Amoco oxidation process
Toray co-oxidation process
Mitsubishi Kasie multistage oxidation process
Eastman multistage oxidation process
36
P-xylene is the feedstock for most of TPA processes while acetic acid in water is the reaction
solvent. Air is compressed to supply oxygen to the reaction and is added in excess to minimize
formation of by-products, achieve high p-xylene conversion and provide measurable oxygen
partial pressure.
Figure 2- 2 Reaction Scheme[3]
TPA is produce by catalytic liquid-phase reaction. The reaction is highly exothermic, releasing
5.3×107 kJ per hour p-xylene reacted, that is removed by allowing the acetic acid solvent to
boil and rest of heat is removed through external jacket. Oxidation of the methyl groups occurs
in three steps. Two intermediates are formed through the reaction, p-toluic acid and 4-
formylbenzoic acid and finally TPA is produce.
2-5 Process Description
Detail of the above listed processes are mention below. It includes their respective operating
temperature pressure conditions and choice of catalyst as well.
2-5-1 Toray process
Toray process, which developed in the late 60s, is considered as a modification on Amoco
process. It was established in two main factories all over the world; one of them in
market considerations for by-products obtained from the process.
This process is based on co-oxidation of p-xylene in an aldehyde liquid medium such as

acetaldehyde to produce a reasonable yield of pure fiber grade TPA. Air is used as a source
of Oxygen and Cobalt or Manganese must be used to form the liquid catalytic acetate
solution. Catalyst and feed are fed into the head of a bubble column while air is introduced.
The Toray process is characterized by the high temperature 100 - 150 °C, which in some
cases may reach 240 °C, and high pressure 500 2000 kPa. The TPA formed is removed
as a suspension in acetic acid then separated and purified.
37
The problem that led to the discontinuing of licensing this process is the huge amount of acetic
acid by product obtained, usually 0.5 - 1.1 ton acetic acid per ton TPA, which makes it suitable
only for high market demand of acetic acid as a requirement[3].
2-5-2 Mitsubishi Kasei process
In mid-1970, Mitsubishi Kasei developed an oxidation process to obtain high yield pure forms
of TPA without a separate purification step in which these products are called medium purity
TPAs. This process is used to reduce the 4- formyl benzoic acid concentration to 200 - 300
ppm in order to obtain suitable feed stock of TPA for polyester industry. This is done by very
intensive oxidation and the separation step is eliminated as the high purity of feedstock is not
critical. The product is often called medium purity TPA and accounts for about 11% of the
TPA produced all over the world. The oxidation process is the same as of Amoco oxidation
where p-xylene, acetic acid, and catalyst are the reaction mixture to form the TPA. It differs
from Amoco in number of oxidation reactors (two vessels), conditions and residence time
(more than 2.5 hrs.) [3].
The second oxidation vessel operates at higher temperature than the first one in order to oxidize
p-xylene - acetic acid mixture in presence of catalyst to TPA. Where the solubility of TPA is
increased with heating, the crystals dissolved with heating. Also at higher temperature acetic
acid tends to be oxidized largely to carbon oxides and water.
Although the TPA is not completely soluble at the higher temperature, the crystals are digested.
So the amount of the released 4-formylbenzoic acid decreases into solution and this means that
the oxidation is completed so the need for a separate purification process is eliminated. The
rest of the Mitsubishi process consists of solid liquid separation and drying to obtain the
powdered product and acetic acid recycled to the process after dehydration [3].
2-5-3 Eastman Process
This process is proven suitable for the production of all kinds of fiber and bottle PET without
limitations at international first grade quality specs. P-xylene is the feedstock with air as
oxidizing agent and acetic acid as a solvent. The reaction is catalyzed by Co +2, Mn+2 and
bromide. The solvent to hydrocarbon weight ratio in the oxidation reactor is in the range of 3 -
5. The catalyst is usually 0.1-0.2 wt % of the solvent used. The temperature and pressure inside
the reactor are in the range of 185 204 °C and 1200 1750 kPa. The maximum recovery
exceeds 95%.
38
The residence time is less than 1 hr to accomplish complete conversion and about 98.3% yield
is achieved. In addition to that, power generation from the process may reach 10,000 kW.
Wash acid tank serves as the acetic acid reservoir that supplies acid deficiency in the feed
stream to the oxidizer reflux tank and the filtrate tank. The filtrate tank collects the prepared
catalyst solution, hydrogen bromides as well as filtrate from the filtrate treatment. The filtrate
is used to control catalyst and acid concentrations. These all and p-xylene are fed together into
the oxidizer. The weak acid stream from the oxidizer reflux tank is sprayed into the top of the
oxidizer in order to prevent solid formation. The oxidizer is a bubble column reactor. A
centrifuge is used to remove impurities from the CTA by the lean solvent that is obtained as
the bottoms of the water removal column. This lean solvent consists of mixture of the oxidizer's
overhead vapor (water, acetic acid and nitrogen) and solvent. Only impurities soluble in this
solvent can be removed from CTA. Then CTA is purified to obtain Eastman Purified
Terephthalic Acid (EPTA) in a post oxidation step done in two oxidizers. This process requires
increasing the temperature to increase the conversion of the CTA impurities oxidation. TPA
(TA) with lower impurity content is obtained from this oxidation. Finally, TPA is directed to
crystallizer. Then separated in vacuum flash drum and the solvent is recovered to the oxidizer
reflux tank. EPTA is finally directed to rotary vacuum filter then dryer to get the final product.
The outlet from centrifuge passes to overflow flash drum then to catalyst recovery and filtrate
treatment unit where it is separated to get soluble impurities, insoluble impurities and the CTA
residue. Both insoluble impurities and the CTA residue are burnt in the fluidized bed or buried
in a landfill. The catalyst is recovered to a filtrate tank. The top stream of the water removal
column enters WRC condensers. Then vent gas is separated from waste water in WRC reflux
drum then directed to regeneration thermal oxidizer/ scrubber. The waste water got is directed
to water treatment station [3].
2-5-4 Hydrolysis of DMT
DMT is an important intermediate in the production of TPA through oxidation- esterification

of p-xylene. It is formed through four steps. First, p-xylene is oxidized by oxygen from air to
p-toulic acid in an oxidation reactor. Then, p-toulic acid is esterified with methanol to methyl
p-toulic in an esterification reactor.
Methyl p-toluate is isolated and returned back to the oxidation reactor in which it is oxidized
to MMT, which is esterified to DMT to be purified.
39
Then finally the DMT passes through a hydrolysis stage which consists of two reaction steps,
where first the DMT turns into MMT, and then the MMT turns into TPA to enter
polymerization [3].
Hydrolysis is shown by following Chemical Reaction:
Figure 2- 3 Hydrolysis Reaction[3]
2-5-5 Amoco Process
Purified TPA became commercially available from Amoco Chemical Co. in 1965. Amoco
process involves purification of crude TPA by a separate step to attain the high product purity
required for PET manufacture. This technology is the most used worldwide, but other
processes have been developed and are operating commercially. The feed passes to the
oxidation reactor at which oxidation occurs. Most of TPA precipitates, because of its low
solubility in the solvent. This yields a two- phase system; TPA slurry; solvent with some
dissolved TPA; and vapor consisting of nitrogen, acetic acid, water, and a small amount of
oxygen. The overhead vapors from the reactor are condensed in heat exchangers, and the
condensate is refluxed to the reactor. Steam, which is generated by condensation, used as
heating source in other parts of the process. Oxygen depleted gas from the condensers is
scrubbed to remove most uncondensed vapors.
Oxidation reactor operates at 175 - 225 C and 1500 - 3000 kPa, at residence time about 2.5
hours.The pressure of hydrogenation reactor is held above the vapor pressure of water to
maintain a liquid phase. Catalyst used in oxidation reactor is multivalent heavy metal [3].
40
Mostly, cobalt and manganese are the multivalent heavy-metal catalysts and bromine is the
renewable source for the free radicals. A soluble cobalt manganese bromine catalyst
system is the heart of the process.
This yields nearly quantitative oxidation of the p-xylene methyl groups with small xylene
losses. Various salts of cobalt and manganese can be used, and the bromine source can be
HBr, NaBr, or tetrabromo ethane.
The effluent stream from the reactor contains TPA as slurry. This slurry passes through a
surge vessel that operates at a lower pressure than the reactor. More TPA crystallizes and the
cooled slurry is then ready to be processed at close to atmospheric conditions. The slurry is
fed to a centrifugation unit at which most of water removed from the product. After
centrifugation, one stream is fed to the recovery unit and the other to a rotary drier. Preheated
air is sent to the drier to remove the moisture present in the final product. TPA crystals are
obtained from the drier by 99% purity, then conveyed to storage, from which they are in turn
fed to the purification step [3].
Water formed and some undesirable by-products must be removed from acetic acid solvent.
Mother liquor from the centrifuge is purified in a solvent recovery tower to purify acetic acid.
The purified acetic acid from the top of the tower is recycled to the reactor and combined
with fresh acetic acid and the bottom product can be processed for catalyst recovery and
regeneration. Vents from the oxidation process, are sent to a gas scrubbing tower then to
water removal tower to remove the water formed as the overhead stream which sent to waste
water treatment. Amoco process involves a purification unit to achieve the required purity
before entering the polymerization step. The main impurity in the crude TPA is 4-
formylbenzoic acid (up to 5000 ppm). There are also yellow impurities and residual amounts
of catalyst metals and bromine.
TPA crystals are dissolved in a hot process water to increase its solubility. The slurry formed
contains at least 15 wt. % TPA and the rest are impurities accessible to the purification reaction.
The solution flows through a hydrogenation reactor. Hydrogen is added to the reactor, where
it dissolves in the feed solution.
In the reactor, 4-formylbenzoic acid is hydrogenated, in presence of palladium supported on

carbon as a catalyst, to p- toluic acid reducing its composition to less than 25 ppm.
41
Various colored impurities are hydrogenated to colorless products. The catalyst is highly
selective; the loss of TPA by carboxylic acid reduction or ring hydrogenation is less than 1%.
The more soluble p-toluic acid formed in the reactor, and other impurities, remain in the mother
liquor. After leaving the final crystallizer, the slurry undergoes centrifugation to yield a wet
cake, and the cake is dried to give the product TPA as a free-flowing powder [3] .
TPA is the main product. More than 98% of the p-xylene is converted with a minimum yield
of 95 mole %. Further, this is on a once-through basis. TPA from oxidation process is called
technical or crude grade of phthalic acid, but the purity is typically greater than 99%. It is not,
however, pure enough for the PET production to reach the required degree of polymerization.
In the purification unit over 98 wt. % of the incoming TPA is recovered as purified product.
The purified TPA as a white powder is called polymer grade TPA which is suitable to be used
in the production of PET[3].
2-6 Steps Involved in Amoco Process
2-6-1 Process feedstock
The process feedstock is p-xylene dissolved in acetic acid with the inclusion of bromide,
manganese and cobalt salts as catalysts[5].
2-6-2 Oxidation
groups produces crude terephthalic acid (CTA). The CTA is largely insoluble, and
consequently the reactors contain significant amounts of solid product crystals. The main
impurity of the CTA relative to PTA is determined
content[5].
2-6-3 Crystallization, filtration and drying
Flash cooling further crystallizes product from the slurry. The solid CTA is then separated and
dried, before being re-slurried in water in preparation for purification[5].
2-6-4 Purification (hydrogenation)
CTA purification proceeds by hydrogenating the 4-

o
aid dissolution, before progressing to the hydrogenation reactor, where the addition of
42
hydrogen initiates the following reaction. The p-toluic acid is much more soluble in water than
terephthalic acid, allowing the PTA to crystallize from solution by flash cooling while the p-
toluic acid remains dissolved. Filtration, washing and drying follow to give solid PTA[5].
2-7 Market of PET
PET is one of the major polymers produced worldwide representing about 18 % of world
polymer production and comes in third after polyethylene and polypropylene. PET production
profitability study is overviewed based on both local and global market.
2-8 Global Production of PET
Global production of PET in 2008 was approximately 50 million MTA. The main downstream
industries based on PET are production of polyester fibers, accounting for around 65% of
global consumption, and PET bottle resins consuming around 30%. Other applications occupy
the remaining fraction containing polyester film and polyester engineering resin[3].
The following pie chart illustrates:
Figure 2- 4 Global Production of PET [3]
2-9 Worldwide Major Producers
Major producers are China Petrochemical Corporation (Sinopec), Reliance Industries, Formosa
Plastics Group, Gruppo Mossi & Ghisolfi, Far Eastern Textile and Alfa Group, and Eastman
chemicals in America[3].
43
2-10 Global market forecast for PET
per year with beverages continuing to be the dominant outlet.
Global demand is predicted to grow up to 17.3 million MTA in 2011. Strong growth in demand
combined with low entry barriers has attracted far too much capacity, especially in Asia.
Figure 2- 5 Growth rate of PET per year [3]
It was estimated that production in the last five years has grown at an average of 10.5% per
year to reach 15.8 million MTA in 2006. However, the forecast capacity growth is 4.5% per
year, in the next five years it will be lower than demand growth, improving operating rates.
Capacity is expected to reach 19.6 million MTA in 2011. Most of the capacity growth has
occurred in Asia with the majority of plants being built in China. According to market forecast
Asia will continue to produce the greatest capacity for the next few years and will be a major
exporter as it takes advantage of its low cost position[3].
2-11 Raw Materials Worldwide
Production of PET is mainly divided into two stages; the first stage is PTA production using
p-xylene as a raw material in presence of acetic acid as a solvent. The second stage is the
reaction between PTA and MEG forming PET. Hence the feedstock for PET production is p-
xylene, acetic acid, and MEG[3].
2-11-1 P-xylene
Isolation of p-xylene accounted for 82% of 41.6 million MTA in 2008 of global mixed xylenes
consumption.
44
Asia is the largest p-xylene producing region, with 64% of capacity; North America produces
20% and Western Europe 9%. Global production of p-xylene in 2008 was approximately 28
million metric tons. -
xylene isomer[3].
BP is another major producer of mixed xylenes and the second-largest producer of p-xylene
and a major producer of its derivative, TPA. China Petrochemical Corporation and its affiliates
have become the second largest producer of mixed xylenes[3].
2-11-2 Acetic acid
The largest use of acetic acid is the manufacture of vinyl acetate monomer which represents
33% of the total production; the second largest derivative is the production of PTA which
represents 22% of the total production which is used to produce PET bottle resins and polyester
fiber. Consultants to grow at 3-4% per year forecast global demand for acetic acid. Growth is
much higher in Asia, pulled by strong demand in China. India is also seen as a country where
there could be strong acetic acid demand growth in the future.
The two biggest producers of virgin acetic acid are Celanese and BP Chemicals. Other major
producers include Millennium Chemicals, Sterling Chemicals, Samsung, Eastman, and Svensk
Etanolkemi[3].
2-12 Kinetic Study for Production of TPA
A fractional kinetic model for the liquid-phase oxidation of p-xylene to terephthalic acid
catalyzed by cobalt acetate and manganese acetate and promoted by hydrogen bromide.
Cincotti studied the kinetic scheme at low temperature and assumed that all the reactions were
zeroth order with respect to gaseous reactants under the condition that the oxygen partial
pressure was higher than a minimum value and first order with respect to liquid reactants. Yan
studied the oxidation kinetics at high temperature and assumed that all the reactions were 0.65th
order with respect to PX and first order with respect to the other liquid reactants, and the effect
of oxygen partial pressure on the reaction rate was neglected[6].
2-13 Uses of Purified Terephthalic Acid (PTA)
Virtually the entire world's supply of terephthalic acid and dimethyl terephthalate are consumed
as precursors to polyethylene terephthalate (PET). World production in 1970 was around 1.75
million tons[3].
45
By 2006, global purified terephthalic acid (PTA) demand had exceeded 30 million tons. A
smaller, but nevertheless significant, demand for terephthalic acid exists in the production of
polybutylene terephthalate and several other engineering polymers[7, 8].
Other Uses are
Polyester fibers based on PTA provide easy fabric care, both alone and in blends with
natural and other synthetic fibers. Polyester films are used widely in audio and video
recording tapes, data storage tapes, photographic films, labels and other sheet material
requiring both dimensional stability and toughness.
Terephthalic acid is use in paint as a carrier.
Terephthalic acid is use as a raw material to make terephthalate plasticizers.
It is used in the pharmaceutical industry as a raw material drugs.
In addition to these end uses, Terephthalic acid based polyesters and polyamides are
also used in hot melt adhesives.
PTA is an important raw material for lower molecular weight saturated polyesters for
powder and water-soluble coatings.
In the research laboratory, terephthalic acid has been popularized as a component for
the synthesis of metal-organic frameworks.
The analgesic drug oxycodone occasionally comes as a terephthalate salt; however, the
more usual salt of oxycodone is the hydrochloride. Pharmacologically, one milligram
of terephthalas oxycodonae is equivalent to 1.13 mg of hydrochloridum oxycodonae.
Terephthalic acid is used as a filler in some military smoke grenades, most notably the
American M83 smoke grenade and M90 vehicle-employed smoke grenade, producing
a thick white smoke that acts as an obscurant in the visual and near-infrared spectrum
when burned.
46
PROCESS DESCRIPTION AND SELECTION
2-14 Production processes

There are several types of production processes used for the industrial production of Tere-
phtahlic acid (TPA).
2-15 Henkel Process (Rearrangement of Benzoic acid and Phthalic

anhydride)
Henkel I technology, which developed to the industrial stage by Teijin Hercules Chemical Co.
and Kawasaki Kasei Chemicals Ltd in Japan, is based on the potassium salts isomerization of
phthalic acids. At present, this process is considered as an obsolete process and no industrial
plants employ this process as its uneconomical in comparison with other methods. [9]
This process is considered as a different route for production of TPA starting with phthalic
anhydride or its precursor, o-xylene or naphthalene vapors, as the raw material. According to
this process phthalic anhydride, which is mainly produced through vapor phase catalyzed
oxidation of o-xylene or naphthalene in presence of V2O5 as a catalyst, is converted
sequentially to mono-potassium and then dipotassium o-phthalate by aqueous recycle of mono-
potassium and dipotassium terephthalate.
The dipotassium o-phthalate is recovered and isomerized into dipotassium p-phthalate in

carbon dioxide and in the presence of Zn-Cd catalyst at a pressure of 10 - 15 bar and at 350
450 °C according to the following equation.
Figure 2- 6 Catalytic Isomerization of dipotassium o-phthalate[10]
Then, dipotassium p-phthalate is converted into TPA by two methods. In the first one TPA
may be formed in two steps as shown in the following equations:
47
Figure 2- 7 Two-step conversion to TPA reaction from dipotassium p-phthalate[10]
The aqueous solution of the acid potassium phthalate obtained by second step reaction is
recycled for use in first step reaction, and the aqueous solution of potassium phthalate obtained
in 1st step reaction is recycled for use as the starting material of thermal rearrangement reaction
after being dried by evaporation or by spraying. TPA produced may be purified by dissolving
it in alkalis and precipitating it from alkaline solution with acids.
The other method for producing TPA is by blowing carbon dioxide into an aqueous solution of
potassium terephthalate to produce acid potassium salt of TPA (precipitate) and potassium
carbonate (in mother liquor), and then the acid potassium salt of TPA is reacted with phthalic
acid or anhydride in an aqueous phase so as to produce TPA (precipitate) and an acid potassium
salt of phthalic acid (in mother liquor). A solution, of which main component is potassium
phthalate, can be obtained by mixing the two mother liquor and boiling to expel carbon dioxide.
The resultant solution can be recycled and reused for preparation of the aqueous solution
containing crude potassium terephthalate and potassium phthalate, which is to be subsequently
concentrated.
2-16 Ammoxidation of p-xylene (Lummus process)

Ammoxidation process for the production of TPA from p-xylene was first licensed by Lummus
then modified by Esso by adding oxygen in the ammoxidation process; this modification
enabled the technology to be commercialized.
48
This process is done by first reacting p-xylene with ammonia on a catalyst producing TPN, and
then the intermediate TPN goes through a hydrolysis reaction where it produces TPA and
ammonia.
Figure 2- 8 Ammoxidation of p-xylene[10]
At first TPN is produced from p-xylene which is passed with ammonia and oxygen over a
catalyst, oxygen is used to regenerate the catalyst in place. The catalyst used in Lummus
process can be Vanadium, molybdenum or other metals while the catalyst used in Esso process
is chromia and vanadia supported on alumina, which is the mostly used catalyst for this process.
Then TPA is produced from TPN by aqueous hydrolysis in the presence of Silica gel or silica
alumina supported on phosphoric acid as a catalyst. The produced acid is produced in the
gaseous phase.
2-17 Amoco Process
Purified TPA became commercially available from Amoco Chemical Co. in 1965. Amoco
process involves purification of crude TPA by a separate step to attain the high product purity
required for PET manufacture. This technology is the most used worldwide, but other processes
have been developed and are operating commercially.
Most of TPA precipitates, because of its low solubility in the solvent. This yields a three phase
system; solid TPA crystals; solvent with some dissolved TPA; and vapor consisting of nitrogen,
acetic acid, water, and a small amount of oxygen. The overhead vapors from the reactor are
condensed in heat exchangers, and the condensate is refluxed to the reactor. Steam, which is
generated by condensation, used as heating source in other parts of the process. Oxygen
depleted gas from the condensers is scrubbed to remove most uncondensed vapors[11].
Oxidation reactor operates at 175 - - 3000 kPa, at residence time about 2.5
hours. Reactor is lined with titanium to withstand the highly corrosive bromine and acetic acid.
49
The pressure of hydrogenation reactor is held above the vapor pressure of water to maintain a
liquid phase.
Catalyst used in oxidation reactor is multivalent heavy metal. Mostly, cobalt and manganese
are the multivalent heavy-metal catalysts and bromine is the renewable source for the free
radicals. A soluble cobalt manganese bromine catalyst system is the heart of the process.
This yields nearly quantitative oxidation of the p-xylene methyl groups with small xylene
losses. Various salts of cobalt and manganese can be used, and the bromine source can be HBr,
NaBr, or tetra-bromoethane. This catalyst system is used in about 70% of the p-xylene
oxidation processes, and this percentage increases as new plants employ it.
The effluent stream from the reactor contains TPA as slurry. This slurry passes through a surge
vessel that operates at a lower pressure than the reactor. More TPA crystallizes and the cooled
slurry is then ready to be processed at close to atmospheric conditions. The slurry is fed to a
centrifugation unit at which most of water removed from the product.
After centrifugation, one stream is fed to the recovery unit and the other to a rotary drier.
Preheated air is sent to the drier to remove the moisture present in the final product. TPA
crystals are obtained from the drier by 99% purity, then conveyed to storage, from which they
are in turn fed to the purification step.
Water formed and some undesirable by-products must be removed from acetic acid solvent.
Mother liquor from the centrifuge is purified in a solvent recovery tower to purify acetic acid.
The purified acetic acid from the top of the tower is recycled to the reactor and combined with
fresh acetic acid and the bottom product can be processed for catalyst recovery and
regeneration. Vents from the oxidation process, are sent to a gas scrubbing tower then to water
removal tower to remove the water formed as the overhead stream which sent to waste water
treatment.
Amoco process involves a purification unit to achieve the required purity before entering the
polymerization step. The main impurity in the crude TPA is 4-formylbenzoic acid (up to 5000
ppm). There are also yellow impurities and residual amounts of catalyst metals and bromine.
TPA crystals are dissolved in a hot process water to increase its solubility. The slurry formed
contains at least 15 wt% TPA and the rest are impurities accessible to the purification reaction.
The solution flows through a hydrogenation reactor. Hydrogen is added to the reactor, where
it dissolves in the feed solution.
50
In the reactor, 4-formylbenzoic acid is hydrogenated, in presence of palladium supported on

carbon as a catalyst, to p-toluic acid reducing its composition to less than 25 ppm.
Various colored impurities are hydrogenated to colorless products. The catalyst is highly
selective; the loss of TPA by carboxylic acid reduction or ring hydrogenation is less than 1%.
After reaction, the solution passes to a series of crystallizers where the pressure is sequentially
decreased. This results in temperature reduction, and crystallization of the TPA.
The more soluble p-toluic acid formed in the reactor, and other impurities, remain in the mother
liquor. After leaving the final crystallizer, the slurry undergoes centrifugation to yield a wet
cake, and the cake is dried to give the product TPA as a free-flowing powder. TPA is the main
product. More than 98% of the p-xylene is converted with a minimum yield of 95 mol%.
Further, this is on a once-through basis. TPA from oxidation process is called technical or crude
grade of phthalic acid, but the purity is typically greater than 99%. It is not, however, pure
enough for the PET production to reach the required degree of polymerization.
In the purification unit over 99.99 wt% of the incoming TPA is recovered as purified product.
The purified TPA as a white powder is called polymer grade TPA which is suitable to be used
in the production of PET[10].
2-18 Du Pont process
It was the first industrial process to manufacture TPA. This process was industrialized by Du
Pont which employs the liquid phase oxidation of p-xylene by nitric acid at 165 °C and 1000
kPa, by the following overall reaction:
Figure 2- 9 Acid oxidation of p-xylene[10]
The TPA formed is separated by precipitation and centrifuging. After drying it is esterified by
methanol at 150 °C in the presence of sulfuric acid catalyst. Although the total yield is 90
molar%, the presence of nitrogen compounds makes purification difficult and nitrogen oxides
recovery encumbers the economics of the system [10, 12-14].
51
2-19 Process selection
A brief comparison of the discussed processes will help us understand that why we selected
the respective process as our production process. The comparison is done in tabular form in
order to fully understand the selection (side by side comparison).
Table 2- 2 Process comparison[14]

Processes Product purity Operating Catalyst
conditions
Cobalt
Amoco process >99% 200oC Manganese
16 bars &
HBr promotor
Vanadium pentoxide
Lummus process* 90% 400-450 oC supported on
Aluminum oxide
Product contains
Du pont process impurities as 148- Auto Catalytic
nitrogenous 8.6-13.7 bar
compounds
Henkel process 95-98% 350 450 oC Zinc & Cadmium

10-15 bars
*This process is not yet industrialized
Amoco Process
the following factors:
Product purity is 99.99%

Solvent recovery is possible
Catalyst recovery is possible
Process is overall very economical
Pollutants emissions are minimum
52
2-20 Process Description

2-20-1 Crude TPA Section
Para xylene, acetic acid and the CMB catalyst (Cobalt acetate, Manganese acetate and
Hydrogen bromide acid) are all mixed together at an ambient temperature of 25oC. The mixture
is then introduced into the reactor by passing it through a pump and a pre-heater which raises
its pressure and temperature to 200oC and 16 bar respectively. Moreover, pre-treated air is
compressed to 16 bars, then cooled to 200oC and is introduced into the reactor. The reaction
occurs at 200oC and 16 bar pressure producing TPA, 4-CBA* (as impurity) and water. Due to
the exothermic heat of reaction, the acetic acid is vaporized and it is purged out with unreacted
air. The acetic acid is then condensed and recycled into the reactor.
The product stream flows to a crystallizer where it throttled to atmospheric pressure and some
flash to vapor phase. The product stream is crystallized by creating super-
saturation through evaporation. The flash acetic acid, water and p-xylene are also condensed
and are sent to the recovery section. The slurry from crystallizer is further passed through a
centrifuge and a drier to remove remaining acetic acid, p-xylene and water. Finally, a 99%
product is obtained at the end of the crude TPA production section. The product majorly
contains TPA and minor amounts of 4-CBA as impurity.
2-20-2 Purified TPA section
The Crude TPA is further treated to remove the remaining 4-CBA impurity in the purification
section. In this section, the Crude TPA is mixed with water again to make a diluted slurry. It is
then motivated to 40 bar and heated to 235oC and introduced into the reactor. The other reactant
is pure Hydrogen gas which also compressed to 40 bar, cooled to 235oC and then it is also
introduced into the reactor. The reaction occurs and the maximum amount of 4-CBA is
converted into p-toulic acid. The p-toulic acid is soluble in water and is easy to remove as
compared to 4-CBA. The Product slurry is then crystallized at a lower temperature of 25oC and
atmospheric pressure in order to crystallize a pure product. Almost all the P-toulic acid remains
in water and the Purified TPA is then centrifuged and dried in order to obtain a 99.99% pure
TPA product[14].
53
2-20-3 Process Flow diagram
Figure 2- 10 Process Flow Diagram
54
Process flow diagram description

Item P- P-102 P-103 M-101 P-104 H-101 CS-101 H- R-101
# 101 102
Name P-xy Acetic CMB Feed Feed Feed Air Air Reactor
pump acid catalyst mixer Mixture Pre- compressor cooler (CSTR)
pump pump pump heater
Item H-103 GL-101 P-105 V-101 CR-101 H-104 CE-101 D-

# 101
Name Vapor Gas Condensate Throttle Crystallizer Flash Centrifuge Dryer
Condenser Liquid pump valve vapor
Separator condenser
Item P-201 T-201 P-202 H-201 CS-201 H-202 R-201 V-201 CR-201
#
Name Water Re- Slurry Slurry Hydrogen Hydrogen Reactor Throttle Crystallizer
Pump Slurry Pump Pre- compressor cooler (Fixed valve
Tank heater bed)
Item # H-203 P-203 CE-201 DR-201
Name Flash Crystal Centrifuge Dryer

vapor slurry
condenser pump
2-21 Plant capacity

The demand of Terephthalic acid globally has increased in the recent years. For Pakistan, these
numbers have seen a significant increase.
For example, in the annual reports of Lotte chemicals Pakistan ltd. they mentioned that the
local polyester industry demand of TPA has increased 10% from 2017 to 2018. The chart shows
the comparison of TPA demand, production of Pakistan and operating rates of the Lotte
Chemicals Pakistan ltd[15].
55
Figure 2- 11 TPA Demand Chart[15]
The total demand of TPA of Pakistan is 780,000 MT per year as of 2018. The Lotte Chemicals
have a plant of a capacity of 500,000 MT TPA per year. They are the sole bulk producers of
TPA in Pakistan. Moreover, Pakistan is still importing the deficit amount TPA from
neighboring countries like China.
From the above discussion and data, we selected the capacity of 265 MT per day. We will be
complete about 12% demand of TPA in Pakistan[15].
56
CHAPTER 3
Material
&
Energy Balance
3 MATERIAL & ENERGY BALANCE
3-1 Feed Mixing Tank Material Balance
Figure 3- 1 FMT material balance
Basis: 1-day operation

3-1-1 Assumptions
Steady state process

3-1-2 General Material Balance Equation
Accumulation = Input - Output + Generation - Consumption

Accumulation = 0
Generation =0
Consumption = 0
Input = Output
Table 3- 1 FMT Material Balance

Inlets Outlets
Components Flowrate (kg/day) Component Flowrate (kg/day)
p-xylene 175720 Mixture 374932.602
Acetic acid 198800.63
CMB 411.973
Total 374932.602 374932.602
58
3-2 CSTR Reactor 1 Material Balance
Figure 3- 2 CSTR Reactor 1 material balance
3-2-1 Assumptions
Steady State
3-2-2 General Material Balance Equation
Accumulation = Input - Output + Generation Consumption

Accumulation = 0
Consumption = 0
Input = Output + Generation
C8H10+3O2 8H6O4+2H20
P-xylene TPA
C8H10+2.5O2 8H6O3+2H20
4-CBA
Conversion = 98%
Table 3- 2 CSTR Reactor 1 material balance

Inlets
F7(kg/day) F1 Flowrate F2 Flowrate
(kg/day) (kg/day)
125244.3 p-xylene 1757200 Oxygen 162080.8
Acetic acid 73557.2 Nitrogen 533516.1
CMB 411.9
Total 249688.2 695596.955
Total input 1070530.5
59
Table 3- 3 CSTR Reactor 1 material balance

Outlets
F3 Flowrate (kg/day) F4 Flowrate (kg/day)
Acetic acid 178920.567 CMB 411.97
Oxygen 8951.523 Water 58446.347
Nitrogen 533516.115 p-xylene 3514.40
CTA 242536.404
4-CBA 24353.563
Acetic acid 19880.06
Total output 1070530.56
3-3 Condenser and Gas Liquid separator Material Balance
Figure 3- 3 Condenser 1 and Gas Liquid Separator material balance
Table 3- 4 Condenser 1 material balance

Inlets Outlets
Acetic Acid 178920.567 Oxygen 8951.523
Oxygen 8951.523 Nitrogen 533516.111
Nitrogen 533516.112 A.A (Vapors) 53676.170
A.A(Liquid) 125244.396
Total input 721388.202 Total output 721388.202
60
Table 3- 5 Gas Separator material balance

Inlets Outlets
F5 Flowrate F6 Flowrate F7 Flowrate
(kg/day) (kg/day) (kg/day)
Oxygen 8951.523 Oxygen 8951.523 A.A(l) 125244.39
Nitrogen 533516.111 Nitrogen 533516.111
A.A (Vapors) 53676.170 A.A (Vapors) 53676.170
A.A(Liquid) 125244.396
3-4 Crystallizer and De-Engaging Vessel material balance
Figure 3- 4 Crystallizer and De-Engaging Vessel material balance
*Key note
Internal jacketed crystallizer
Partial condenser of efficiency 70%
61
Table 3- 6 Crystallizer 1 material balance

F CMB WATER P- CTA 4-CBA Acetic
Inlets Xylene acid
Flowrate 411.97 58446.347 3514.40 242536.404 24353.563 19880.06
(kg/day)

Outlets
CMB 0 CMB 411.972 CMB 411.972
Water 52799.475 Water 5646.869 Water 42606.502
p-xylene 29.837 p-xylene 3484.562 p-xylene 3505.448
CTA Negligible CTA 242536.404 CTA 242536.404
4-CBA Negligible 4-CBA 24353.563 4-CBA 24353.563
Acetic acid 1782.168 Acetic acid 294531.268 Acetic acid 19345.412
Table 3- 8 Partial Condenser 2 material balance

Inlets Outlets
Flowrate (kg/day) F8" Flowrate (kg/day)
CMB 0 Water (vapors) 15839.842
Water 52799.475 Water (liquid) 36959.632
p-xylene 29.837 p-xylene(vapors) 8.951
CTA Negligible p-xylene(liquid) 20.886
4-CBA Negligible Acetic acid(vapors) 534.650
Acetic acid 1782.168 Acetic acid(liquid) 1247.517
Total 54611.481 54611.481
62
Table 3- 9 De-Engaging Vessel material balance

Inlets Outlets
F8" Flowrate (kg/day) F8* Flowrate F9 Flowrate
(kg/day) (kg/day)
Water (v) 15839.842 Water (v) 15839.842 Water (l) 36959.632
Water (l) 36959.632 P-xylene(v) 8.951 p-xylene(l) 20.886
P-xylene(v) 8.951 Acetic 534.650 Acetic 1247.517
acid(v) acid(v)
p-xylene(l) 20.886
Acetic 534.650
acid(v)
Acetic 1247.517
acid(l)
3-5 Centrifuge 1 material balance
Figure 3- 5 Centrifuge 1 material balance
*Key note
F11 streams goes to the recovery section
Efficiency of centrifuge 70%
63
Table 3- 10 Centrifuge 1 material balance

Inlets Outlets
CMB 411.972 CMB 411.972 CTA 242536.404
Water 42606.502 Water 29824.551 4-CBA 24353.563
p-xylene 3505.448 p-xylene 3505.448 Water 12781.950
CTA 242536.404 CTA 0
4-CBA 24353.563 4-CBA 0
Acetic acid 19345.412 Acetic acid 19345.412
3-6 Dryer 1 material balance
Figure 3- 6 Dryer 1 material balance
Table 3- 11 Dryer 1 material balance

Inlets
F12 Flowrate (kg/day) Flowrate (kg/day)
CTA 242536.404 Air 58000
4-CBA 24353.563
water 12781.950
64

Outlets
Air + water 70781.950 CTA 242536.404
4-CBA 266889.968
3-7 Re-Slurry Tank and Reactor 2 Material balance
Figure 3- 7 Re-Slurry Tank and Reactor 2 material balance
*Key Note
Fixed bed catalytic reactor
Conversion = 99%
C8H6O3 + 2H2 8H8O2 + H20
4-CBA P-toulic acid
Table 3- 13 Re-Slurry Rank material balance

Inlet Outlets
TA 266889.968 Water 1512376.487 TA + slurry 1779266.455
65
Table 3- 14 Reactor 2 material balance

Inlet
CTA 242536.404 Hydrogen 667.085
4-CBA 24353.563
Water 1512376.486
Table 3- 15 Reactor 2 material balance

Outlet
F18 Flowrate (kg/day) F17" Flowrate (kg/day)
CTA 242536.404 Hydrogen 19.620
4-CBA 243.535
P-toulic acid 21864.482
Water 1515269.581
3-8 Crystallizer and De-Engaging Tank material balance
Figure 3- 8 Crystallizer 2 and de-engaging tank material balance
66

Inlet Outlet
F18 Flowrate F19 Flowrate F20 Flowrate F20 Flowrate
(kg/day) (kg/day) (kg/day) (kg/day)
CTA 242536.404 CTA Negligible CTA 242536.404 CTA 242536.404
4-CBA 243.535 4- Negligible 4- 243.535 4-CBA 243.535
CBA CBA
P-toulic 21864.482 P- Negligible P- 21864.482 P- 21864.48
acid toulic toulic toulic
acid acid acid
Water 1515269.58 Water 1515269.5 Water 0 Water 1060688.707
Total 1779914 1515269.5 264644.42 1325333.129
Table 3- 17 Partial Condenser material balance

Inlet Outlet
F19 Flowrate (kg/day) F19' Flowrate (kg/day)
Water 1515269.58 Water(vapors) 454580.87
Water(liquid) 1060688.707
Table 3- 18 De-Engaging Vessel 2 material balance

Inlet Outlet
F19' Flowrate F19* Flowrate F19'' Flowrate
Water(vapors) 454580.874 Water(vapors) 454580.874 Water(liquid) 1060688.71
Water(liquid) 1060688.71
3-9 Centrifuge 2 material balance
Figure 3- 9 Centrifuge 2 material balance
67
Table 3- 19 Centrifuge 2 material balance

Inlet Outlet
CTA 242536.404 CTA 0 CTA 242536.404
4-CBA 243.535 4-CBA 0 4-CBA 243.535
P-toulic 21864.482 P-toulic acid 0 P-toulic acid 21864.482
acid
Water 1060688.71 Water 742482.094 Water 318206.612
Total 1325333.13 Total outlet 1325333.129
3-10 Dryer 2 material balance
Figure 3- 10 Dryer 2 material balance

Inlet Outlet
F22 Flowrate F23' Flowrate F23 Flowrate F24 Flowrate
(kg/day) (kg/day) (kg/day) (kg/day)
CTA 242536.404 Air 5568000 Air + 5886206.612 PTA 264644.422
Water
4- 243.535
CBA
P- 21864.482
toulic
acid
Water 318206.612
Total 6150851.03
Total 6150851.03 Total output 6150851.034
68
ENERGY BALANCE
3-11 Heat Balance on Pre-Heater H-101
Figure 3- 11 Pre-Heater heat balance
Table 3- 21 Pre-Heater heat balance

Inlet T(K) Outlets T(K) Avg. temp (K) (K)
298 473 385.5 175
Table 3- 22 pre-heater heat balance

Comp. Cp avg (J/kmoleK) Molar flow rates in
(kmole/hr)
Acetic 149497.909 51.039 Heat out of the
acid(L) preheater (j/hr)
P-xylene 213461.284 68.968 1335304166
Air 2.92E+04 1004.965 2576357993
CTA 5.90E+05 Total 5.13E+09
4-CBA 2.47E+05 120.047 Heat duty of
preheater
Water 7.63E+04 9.04E+09
Oxygen 2.99E+04 2511.201
Nitrogen 2.92E+04
Acetic 7.74E+04
acid(V)
CMB 2.23E+06 0.0398
69
3-12 Heat Balance on compressor CS-101
Figure 3- 12 Compressor heat balance
Table 3- 23 Compressor heat balance

Inlet Temp (K) Outlet Temp (K) T avg (K)
298 680 489
Cp avg
382 2.96E+04 1.14E+10
3157.238
3-13 Heat Balance on Cooler CO-101
Figure 3- 13 Cooler heat balance
Table 3- 24 Compressor heat balance

Inlet Temp (K) Outlet Temp (K) T avg (K)
680 473 576.5
Cp avg
-207 3.01E+04 -6.27E+09
-1741.73
70
3-14 Heat Balance on Reactor R-101
Figure 3- 14 Reactor heat balance
Table 3- 25 Reactor heat balance

Comp. CMB Acetic acid P-xylene Air Total
/hr) 1.56E+07 1335304166 2576357993 5.13E+09 9.06E+09 2515.524

Comp. CMB Acetic acid p-xylene 4-CBA Water CTA Total
1.56E+07 412438570.5 51527552.7 2.92E+08 1.81E+09 6.28E+9 2461.37

Comp. J/hr) of purge /hr) of recycle acetic
acid (after Condenser)
Acetic acid(V) 4.64E+09
Oxygen 6.11E+07 2273564568
Nitrogen 4.06E+09 631.545
Total 8.76E+09
2433.060
Q J J/hr) of recycle acetic acid (after Condenser) J/hr) of product

- J molesK) Limit
Q = -26650.35349 kW
71
3-15 Heat Balance on Condenser C-101
Figure 3- 15 condenser heat balance
Condenser duty is given by;
Q = Latent heat + Sensible heat = m
of acetic acid = -22680564.71
Cp = 9.16E+04 J/kmoleK
Q = -571.1930961 kW
3-16 Heat Balance on Crystallizer CR-101:
F8
F9
CR-101
F10
Figure 3- 16 Crystallizer heat balance
72
Table 3- 28 Crystallizer heat balance

Comp Liquid(kmole/hr) Vapors(kmole/hr) B.P (K) at 1 bar
Acetic acid 13.794 1.236 372.6
Water 135.292 122.22
CBA 6.759
CTA 60.826
CMB 0.039
P-Xylene 1.379 0.011
Total Solution 218.091 123.469

After Throttling Liquid Portion (kmole/hr)
Acetic acid 12.557
Water 13.071
CBA 6.759
TPA 60.826
CMB 0.039
in (J/hr) out (J/hr)
s7.09E+09 -7.09E+09

Heat of crystallization (J/kmole) Q(The heat duty of crystallizer
cooler)(J/hr)
-20380264 -1.86E+10
73
F8 F8'
C-102
Figure 3- 17 Condenser heat balance
Table 3- 31 Condenser heat balance

Out (kmole/hr)
Liquid Vapors Cpv Cpl Latent heat
8.66E-01 3.71E-01 8.29E+04 133090.601 23494633.55
85.55470537 36.66 34452.01 195354.383 34999846.96
0.00819772 0.003 1.76E+05 7.53E+04 31129230.61
8.64E+01 3.70E+01
T1 T2
-100.56 -74.6
Duty of condenser(J/hr) -4.57E+09
In kwatt -1270.618176
3-18 Heat Balance on Dryer DR-101
F12
F13' F13
DR-101
F14'
Figure 3- 18 Dryer heat balance
74
Table 3- 32 Dryer energy balance

Comp In Out(same) (K)
Air 83.333 83.333 205
CTA 60.826 60.826 125
4-CBA 29.587 29.587 110
Water 6.759 6.759
J/hr) by air (383K) 495416666.7
J/hr) by air (383K) 357284611.6
J/hr) by cake (408K) 4.75E+09
Heat to be supplied by the system (J/hr) 3.90E+09
n(J/hr) by air (453 K) - (383K) - /hr) by cake (408K)
Q (Heat to be supplied to the system) = 1148.44506 kW
3-19 Heat Balance on Re-Slurry tank
By Mixing Point Formula;
T1, T2, T3 = Temperature of each stream
M1, M2, M3 = Molar flow rates of each stream
Cp1, Cp2, Cp3 = Specific heat capacities of each stream
T1= T2 = 408K, T1 = 298K
T = 313K
75
3-20 Heat Balance on Pre-heater H-201
F16' F16
Figure 3- 19 Pre-Heater 2 heat balance
Table 3- 33 Pre-Heater 2 heat balance

Molar flow in Cp avg (K) Duty of pre-
(kmole/hr) heater
TPA 60.826 5.90E+05 190 6.82E+09
CBA 29.587 2.47E+05 1.39E+09
Water 3500.871 7.96E+07 5.29E+13
Total 5.30E+13
3-21 Heat Balance on compressor CS-201
CS-201
Figure 3- 20 Compressor 2 heat balance
Table 3- 34 Compressor 2 heat balance

Inlet T (K) Outlet T (K) Avg temp (K)
298 961.827 629.914
Flow in (kmole/hr) Cp avg (J/kmoleK)
663.827 13.787 2.93E+04
J/hr) 2.68E+08 74.490
76
3-22 Heat Balance on Reactor R-201
Figure 3- 21 Reactor 2 heat balance
Table 3- 35 Reactor 2 heat balance

Molar flow in Mole flow out (K) Cp avg
(kmole/hr) (kmole/hr)
TPA 60.826 60.826 205 5.90E+05
CBA 29.587 0.067 2.47E+05
Water 3500.871 3507.568 7.96E+07
Hydrogen 13.787 0.405 6.99E+02
P-toluic 6.691 6.99E+02
acid
At = 190K
Table 3- 36 Reactor 2 heat balance
TPA 7.36E+09 TPA 7.36E+09
CBA 1.50E+09 CBA 3.42E+06
Water 5.71E+13 Water 5.72E+13
Hydrogen 8.25E+07 P-toluic acid 9.59E+05
Total 5.71E+13 Hydrogen 2.43E+06
Total 5.72E+13
- /hr) of product 4.39E+09 (J/hr)
1220.491
77
3-23 Heat Balance on Crystallizer CR-201
F19
F18
F19''
CR-201
F20
Figure 3- 22 Crystallizer 2 heat balance
Table 3- 37 Crystallizer 2 heat balance

Molar flow in (kmole/hr) Cp avg (205 K) (K)
TPA 60.826 5.90E+05 205
CBA 0.067 2.47E+05 205
Water 3507.568 7.96E+07 205
P-toluic acid 6.691 6.99E+02
Total solution 3568.394

Molar flow out (kmole/hr) Cp avg (205 K) (K)
TPA 60.826 5.90E+05 -205
CBA 0.067 2.47E+05 -205
Water 3507.568 7.96E+07 -205
P-toluic acid 6.99E+02

(J/kmoleK)
(J/kmoleK)
TPA 7.36E+09 -7.36E+09
CBA 3.42E+06 -3.42E+06
Water 5.72E+13 -5.72E+13
P-toluic acid 9.59E+05 -9.59E+05
Total solution 5.72E+13 -5.72E+13
Q(The heat duty of crystallizer cooler) -1.15E+14
Heat of crystallization (J/kmole) -20380264
78
F19' F19
Figure 3- 23 Condenser 2 heat balance
Table 3- 40 Condenser 2 heat balance

Inlet Temp 503 Cp avg Molar flow Molar flow
(K) in out
(kmole/hr)
Outlet 298 Vapors 34251.680 3507.569 1052.270
Temp (K)
Liquid 7.68E+04 2455.297
Q(Condenser Latent Heat
Duty in J/hr)
-1.25E+11 -130 -75 -
40842163.75
-34820.81
3-25 Heat Balance on Dryer D-201
F22
F23 F23'
DR-201
F24
Figure 3- 24 Dryer 2 heat balance
79
Table 3- 41 Dryer 2 heat balance

Comp. In Out
(J/kmoleK)
CTA 60.826 60.826 4.76E+10
CBA 0.067 0.067
Water 736.589 736.589
P-toluic acid 6.691 6.691
Air 8000 8000
(K) (K)
205 115
Table 3- 42 Dryer 2 heat balance

Comp. Cp avg
(413K) (J/kmoleK) cake(420K)
(J/kmoleK)
CTA 32305043034 6.91E+09 5.90E+05
CBA 2.47E+05
Water 7.68E+04
P-toluic acid 6.99E+02
Air 2.90E+04
(K) (K) (K) Q (J/hr)
205 115 122 8.35E+09
80
CHAPTER 4
Equipment Design
4 EQUIPMENT DESIGN
4-1 Design of Shell and Tube Pre-Heater:

4-1-1 Selection Criteria
Table 4- 1 Heat exchanger comparison

Exchanger type Feature and limitation
Double pipe heat exchanger Capacity : Small scale
Expensive: Less
H.T. area: Maximum
Operate at: High temp. & pressure
Fluid viscosity: Both high/low
Shell and tube heat exchanger Capacity: Large scale
Expensive: Less
H.T. area: Maximum
Operate at: High pressure
Fluid viscosity: Both
Gasket and welded plate exchanger Capacity: Small scale
Expensive: Much
H.T. area: Maximum
Operate at: Low temp. & Pressure
Fluid viscosity: Viscous
Compact heat exchanger Capacity: Large scale
Expensive: Much
H.T. area: Maximum
Operate at: Low pressure & Temperature
Fluid viscosity: Gas-Gas
82
4-1-2 Selection parameter of our design
Table 4- 2 Selection Parameters

Large heat transfer? Yes
High operating pressure? Yes
High operating temperature? No
High viscous fluid? No
Small scale service? No
Maximum allowable area Yes
suitable for our system.
4-1-3 Shell and tube heat exchanger (Configuration Selection):
Table 4- 3 Heat Exchanger Configuration

Fixed tube exchanger Simple
Economical
U-tube type exchanger Expensive at low pressure
Difficult cleaning
Floating head exchanger Can handle both high temperature and

pressure stream.
Cleaning easily
4-1-4 Design Steps of Heat Exchanger:
The main steps of design as follows:
Selection of heat exchanger

Perform energy balance and find out the duty of heat exchanger
Obtain the required properties of hot and cold fluids
Calculate LMTD and true temperature
Assume (Uo) overall heat transfer coefficient and calculate provisional area
83
Configuration selection of tube and shell side

Calculate flow area, mass velocity and Reynolds number
Calculate hi and ho
Calculate Uo to verify the assumption
Calculate the pressure drop
4-1-4 Calculation of heat exchanger:
4-1-4-1 Heat duty:
Where;
m = mass flow rate
Cp = heat capacity
Q = 1680 kW
4-1-4-2 Mass flow rate of steam:
m = 31756 kg/hr
4-1-4-3 Properties of hot steam:
Heat capacity = 1.905 kJ
Viscosity = 0.000192 Pa.s
Density = 8.39 kg/m3
Thermal conductivity = 0.684 W/m
4-1-4-4 Log mean temperature difference:
LMTD = 116 oC
84
4-1-4-5 Assumption:
U = 568 W/m2K
4-1-4-6 Provisional area:
A = 25.42 m2
4-1-4-7 Tube configuration:
From table 10 heat exchanger tube data[16]
BWG = 16
Inside diameter = 0.0157 m
Outside diameter = 0.019 m
Length = 3.66 m
Passes = 2
Area of one tube = 0.218 m2
Number of tube = provisional area/area of one tube
Number of tube = 116
4-1-4-8 Bundle and shell diameter:
Db =
k1 = 0.249
n1 =2.207
Db = 0.3058
Using split ring floating head
85
Bundle diameter clearance = C = 0.052 m[17]
Shell diameter (Ds) = Db + C = 0.3578m
4-1-4-9 Tube side coefficient (Hot fluid):
Tube cross sectional area =
Tube cross sectional area = 0.000193 m2
Tube per pass = 58
Total flow area = 0.0147 m2
Mass velocity = G = mt / at
G =313367 kg/m2hr
Water linear velocity = 37348 m/hr
Reynolds number = NRe =
Reynold s number = 7196
86
4-1-4-10 Overall coefficient:
hi =
hi = 990.925
ho[18] =
ho = 3719.497
1/U = 0.001278
Ud = 782 W/m2 oC
4-1-4-11 Shell side coefficient:
Baffle spacing = Ds/5 = 0.0720 m
Tube pitch = 1.25 Do
Tube pitch = 0.0238
Equivalent diameter = De =
De = 0.0135m
Flow area = As =
Mass velocity = Gt = 3014363 kg/m2hr
Linear velocity = 1.40 m/sec
Reynolds number = NRe = = 16490
4-1-4-12 Pressure drop calculation:
Shell side
At Re = 17237, f = 0.0019 ft2/inch2, jf = 0.0045
87
Ps =
= 6.12 psi
Tube side
At Re = 7196, f = 0.0029 ft2/inch2, Jf = 0.0051 (DQ Kern)
Np = number of passes = 2
1.57 psi
4-1-5 Specification sheet:
Table 4- 4 Heat Exchanger Specification Sheet

Heat transfer area 25.42 m2
Total number of tube 116
Diameter of shell 0.36 m
Overall heat transfer coefficient 568 W/m2 oC
Total pressure drop (shell side) 6.07 psi
Total pressure drop (tube side) 2.032 psi
88
4-2 REACTOR DESIGN

Chemical reactors are vessels that are designed for a chemical reaction to occur inside of
them.
4-2-1 Reactor System

As far as reactor system is concerned it is basically
Liquid phase Air Oxidation of P-xylene
The reaction is highly exothermic
Reactants includes P-xylene, Acetic Acid and Air
Catalyst comprises of salts of cobalt and manganese as cobalt acetate, manganese

acetate
Hydrogen bromide is used as promoter
4-2-2 Overall Reaction

The overall reaction for the production of Terephthalic Acid is as follows:
rH298 = -8.7x105 kJ/kmol
4-2-3 Reaction Operating Conditions

Pressure =16 bar
Temperature =
89
4-2-4 Choice of Reactor

Reactors are classified based upon the following criteria[19]:
Classification
of Reactors
Mode of Phases in
operation contact
Batch Continuous Gas- liquid

Operation Operation Liquid- liquid
Gas solid
Liquid solid
Gas-liquid- solid
Figure 4- 1 Classification of Reactors [20]
As the proposed plant in continuous operation, we choose continuous reactor due to

following reasons:
Handle large quantities
Small Space time
For the production of Purified Terephthalic Acid (PTA) basically our reaction is liquid gas
reaction.
90
The contacting pattern between gas and liquid can be one of the following:
Bubble column (with

gas distribution device)
Gas bubbles dispersed
in continuous liquid
phase
Stirred tank (mechanical
gas dispersion)
Contacting pattern between Liquid droplets

gas and liquids dispersed in continuous Spray reactor
gas phase
Wetted-wall column
Thin flowing liquid

film in contact with gas
Packed column
Figure 4- 2 Classification of Reactors[20]
4-2-5 Pictorial View of the contacting Pattern of Liquid-Gas Reactions [20]
91
4-2-6 Choice of Reactor

Continuous stirred tank reactor favors the following:
Run at steady state
Well mixed
Uniform temperature and concentration throughout the reactor
Good temperature control
92
Favor low order reaction
Commonly used for gas-liquid contact
Mixing eliminates most of the hot spots
4-2-7 Designing of Continuous Stirred Tank Reactor (CSTR)

Following are the steps involved in designing of CSTR:
Calculating the volume of continuous stirred tank reactor using performance equation
as follows
V= Volume of reactor FAo = molar flow rate of component A
XA = Conversion CAo = Initial Concentration of component A
Calculating Space time by the following equation:
= V / Vo
Calculating volume by giving head Allowance.

The range for L/D ratio is 3-5.
The length and diameter of the reactor can be calculated using actual volume of the
reactor.
Volume of cylinder = r 2l
Heat transfer area can be calculated using the following equation
A= 2 rl
4-2-7-1 Mathematical Calculations
P-xylene A component Limiting Reactant
Conversion of P-xylene = 98% = 0.98
Order w.r.t P-xylene = 0.65
93
Figure 4- 3 Lumped kinetic scheme for the oxidation of p-xylene to terephthalic acid[6]
4-2-7-1 Values of rate constant k (min-1)
k1 = 0.216 k2 = 0.863 k3 = 0.0479 k4 = 0.436
Value of k is calculated by this equation[21]:
k = 0.0345 min-1
4-2-7-2 Calculation of CAo
CAo = Moles of p-xylene / Vol. of fluid
CAo = 3.331 kmol/m3
CA = CAo (1- XA) by substituting values I get,
CA = 0.066 kmol/m3
4-2-7-3 Rate Equation
FAo = molar flow rate of p-xylene = 1.150 kmol/min
-ra = k CAn
By putting all values
-ra = 0.0059 kmol/m3 min
4-2-7-4 Design Equation
V = FAo XA / -ra [21]
By putting values,
94
V = 189.732 m3
Approximately,
V = 190 m3
By giving head allowance of 10 % [19]
V = 190×0.10 +190
V = 209 m3
4-2-7-5 Calculating Length and Diameter of the Reactor
Standard L/D ratio = 3 [17]
L=3D D=
D = 4.32 m L = 3D L= 3 4.321 = 12.96 m
4-2-7-6 Available Area
A= 2 rl
A = 2×3.14×2.161×12.963
A = 175.88 m2
4-2-7-7 Jacket Design
Heat of Reaction = -5.2×107
Latent heat of Vaporization of Acetic Acid = 5.394×105 kJ / hr [17]
4-2-7-8 Heat Calculations
Amount of Heat to be removed = H = -14649.816 kW
H = 14.65 MW
4-2-7-9 Choice of Coolant
As the amount of heat to be removed is very large, so water cannot be employed as a

coolant.
For such heat removal, DOWTHERMS is selected.
95
DOWTHERM (eutectic mixture of two very stable organic compounds, biphenyl and
diphenyl oxide).
4-2-7-10 Mathematical Calculations
Conditions to remove heat through external simple Jacket
Area Available = Area Required [19]
Area Available = 175.88 m2
Mass flow rate of coolant is calculated by this equation:
.
Q = mCp T m = Q/Cp T
By putting values;
.
m = 159.42 kg/sec
Calculating T LMTD
T LMTD = 146
Overall Heat Transfer Equation
Q = UA TLMTD
Calculating overall heat transfer coefficient by re-arranging equation
U = Q/A TLMTD
By putting values,
U = 572 W/ m2K
Heat Transfer Coefficients in an Agitated Vessel
For six blade pitched turbine[22];
Where Vi = µ / µw
Inside heat transfer coefficient = hi = 1161 W/ m2.K
96
Outside heat transfer Coefficient (No phase Change)
[18]
De = 0.145 Flow Area = ( /4) De2 = 0.0166 m2
Re = 735798.9 Pr = 23.850
ho = 7781 W/ m2K
Calculating Actual Heat Transfer Coefficient
1/U = 1/hi + x/ kw + 1/ho
U = 571 W/m2K
This implies that,
Area Available = Area Required
Area Required = A = Q / U TLMTD
A = 176 m2
4-2-7-11 Choice of Agitator
Following parameters must be keep in consideration while choosing an Agitator: (McCabe

Smith)
Viscosity of liquid
Degree of Mixing
Power Requirement
RPM
97
Table 4- 5 Choice of Agitator[23]

Factors/ Propellers Paddles Turbine
Type
Viscosity For low to For moderate For low to high viscous fluids
moderate viscous liquids
Viscous liquids
Flow For Axial flow For radial and For radial and Tangential flow,
pattern Tangential Flow sometimes Axial flow also
Types Square pitched Flat paddle, Flat, Curved and Pitched Blade
Marine Propellers Anchor Agitator
Blades 3-blade, 4-blade, 2 and 4 bladed 2-8 Blades, But six blades is used
Toothed paddles as standard
RPM range 400-800, 20-150 50-250
1150-1750
98
Flow Arrangement
For gas liquid, radial flow pattern for gas dispersion as well as Axial for
Heat transfer enhancement and promotion of chemical reaction is required.
Based on this observation I choose pitched blade Turbine for Agitation.
Standard Turbine has six blades.
Range for tip Velocity for liquid gas mixtures is 15 - 20 ft /sec.

(Chemical Process Equipment Selection & Design by Walas)
Figure 4- 4 Pictorial View of Pitched 6-Blade Turbine[23]
99
Design Procedure
Following are the steps involved in designing of Agitator[23]:
Calculating impeller diameter (Da), distance of turbine blades from the tank bottom
(E), width of blades (W) and length of blades (L).
Calculating impeller Reynolds number by the following equation:
NRe = Da2 Nr /
Calculating number of revolutions per minute by using tip velocity relation given by:
V = Da Nr Nr = V/ Da
Calculating the power requirement for Agitator by following relation:
P = Npo Nr3 Da5
Design Parameters of an Agitator
100
Impeller Reynolds Number
Nr = V/ Da V = 5.1 m/s Da = 1.440 m
Nr = 1.133 RPS
NRe = Da2 Nr /
NRe = 9218354
As the Value of Reynolds no. is greater than 10,000 so power number Npo = KT
KT = For turbine six blades = 4.80[18]
Power Requirement for Agitator
P = Npo Nr3 Da5
By putting values;
P = 16 hp
4-2-7-12 Specification Sheet for Agitator
Table 4- 6 Specification Sheet of Agitator

Impeller Diameter Da 1.440 m
Impeller height from the tank bottom E 1.440 m
Length of Impeller Blade l 0.360 m
Width of Impeller Blade W 0.2880 m
Speed of Agitator 68 RPM
Power Consumption 16 hp
101
4-2-7-13 Mechanical Design of Reactor
It includes
Choice of Construction Material
Choice of Head
Design Pressure and Design Temperature
Calculation of Thickness of wall, head and jacket
Choice of Construction Material
Industrially standard material of construction is Stainless Steel[18]
Stainless Steel
Martensitic Austenitic
Ferritic
I have selected Austenitic type Stainless Steel -304 whose maximum allowable
temperature is 900.
For Stainless Steel 304 maximum allowable working stress (k

kPa
102
Choice of Heads
Heads of various shapes close the ends of a cylindrical vessel. The principal types used are[17]:
Hemispherical heads
Ellipsoidal heads
Tori-spherical heads
Decision-making
Standard tori-spherical heads (dished ends) are the most commonly used end closure
for vessels up to operating pressures of 15 bar.
They can be use for higher pressures, but above 10 bar their cost should be compared
with that of an equivalent ellipsoidal head.
Above 15 bar an ellipsoidal head will usually prove to be the most economical closure
to use.
Hemispherical heads are use for high pressures but are not economical. Therefore, I
choose ellipsoidal head for my reactor, as my operating pressure is 16 bar.
Design pressure
A vessel must be designed to withstand the maximum pressure to which it is likely to
be subjected in operation.
For vessels under internal pressure, the design pressure is normally 5 to 10 per cent
above the normal working pressure[17].
Design Pressure = P = 16 × 1.1 = 17.6 bar
Design temperature
The strength of metals decreases with increasing temperature so the maximum allowable
design stress will depend on the material temperature[17].
Maximum Allowable temperature for stainless st
103
Calculating Wall thickness of Cylindrical Shell
The equation used for calculating the wall thickness of cylindrical shell is as follows[18]:
P = Design Pressure, kPa ri = Radius of cylindrical shell, m
Cc = Corrosion Allowance = 2mm S = Maximum allowable working stress, kPa
EJ = Efficiency of joints = fully radiographed = 1
By putting values,
t = 0.0460 m
Calculating Wall thickness of Ellipsoidal head
The equation used for calculating the wall thickness of Ellipsoidal heads is as follows[18]:
Where Da = Diameter of the tank
By putting Values,
t = 0.047 m
104
4-2-7-14 Specification Sheet for Continuous Stirred Tank Reactors
Table 4- 7 Specification Sheet of Agitator

Working Volume 190 m3
Design Volume 209 m3
Process Temperature
Design Temperature
Working Pressure 16 bar
Design Pressure 17.6 bar
Diameter of Reactor 4.321 m
Length of Reactor 12.963 m
Length to Diameter ratio 3
Type of Head Ellipsoidal
Type of Agitator Pitched six blade Turbine
Cooling Arrangement Simple Jacketed
Wall thickness of Reactor 0.0460 m
105
4-3 DESIGNING OF DRYER

It includes the following steps.
Brief Introduction
Classification of dryers
Selection of dryer
Brief description of selected dryer
Design considerations
4-3-1 Brief Introduction
In general, drying a solid means the removal of relatively small amounts of water or other
liquid from the solid material to reduce the content of residual liquid to an acceptably low
Drying is usually the final step in a series of operations, and the product from a dryer is often
ready for final packaging. In a dryer, Water or other liquids are removed from solids thermally
by vaporization.
4-3-2 Classification of Dryers

Drying equipment may be classified in several ways. The two most useful classifications are
based on
The method in which solid is directly exposed to the hot gases (usually air).
The method in which heat is transferred to the solid from an external medium such as
condensing steam, usually through a metal surface with which the solid is in contact.
Dryers that expose the solids to the hot gases are called adiabatic or direct dryers while
those in which heat is transfer from the external medium are known as non-adiabatic or
indirect dryers[23].
106
4-3-3 Selection of dryer
4-3-3-1 From Classification No. 1
1) Indirect Heat Dryers are selected, because
In current design, direct heat dryer is used as per the assumptions of no

explosive mixture occurrence and no dusting problems. Whereas both the
problems are possible while dealing with the CTA powder. So, indirect heating
dryer is used to solve this problem.
The material to be handled is not heat sensitive.
2) Continuous Dryers are selected, because
For throughputs greater than 50,000 Kg/day, continuous dryers are used. So
indirect Heat Continuous Dryers are selected.
4-3-3-2 From Classification No. 2
3) Rotary Dryer is selected, because
Suitable for crystalline, granular or fibrous solids.

Used for High capacity/High production rate.
Thermal Efficiency Range is 55 75%.
Low operating Cost
Most Economical in Construction
Known as Workhorse of Process Industry
Low maintenance cost
So indirect Heat Rotary Dryer Is Selected.
4-3-4 Indirect Heat Rotary Dryer
It consists of a cylinder, rotated upon suitable bearings and usually slightly inclined to
the horizontal.
Wet feed enters one end of the cylinder progress through it by virtue of rotation and
slope of the cylinder and discharge as finished product at the other end.
In this dryer solids are directly exposed to hot gas usually air[23].
107
Figure 6- 3- 1 Indirect Rotary Heat Drier[23]
A-dryer shell, B-shell supporting rolls, C-drive gear, D-Air discharge hood, E- discharge fan, F- feed chute,
G-lifting flights, H-Product discharge, J-Air heater
4-3-5 Design Considerations

General design considerations for direct heat Rotary dryer are:
Solid Feed Rate and Moisture Content
Drum Diameter and Length
Drum Slope
Rotational Speed
Lifting Flights
Residence Time
Outlet Humidity
4-3-6 Solid Feed Rate and Moisture Content
Solid feed rate
F12 = ms = 97.224 kmol/hr
Moisture Contents
Moisture contents=Mass of water/Mass of dry solid
Initial moisture content = 12781.9508/ 266890
108
Xa = 0.0478= 4.78 %
Final moisture content = 0
Xb = 0 %
4-3-7 Temperature Selection & Calculations
Temperature of air
Inlet air temperature (Ta)
We are using steam heated air for drying and for this air inlet temperature varies (given in
M from 120 to 175 Co
The higher the temperature of inlet gas stream, the higher the efficiency of the dryer in general.
So take inlet air temperature= Ta = 148 C0 =421K
4-3-8 Humidity of Inlet air (H1)
Inlet humidity of air is found with the help of dry bulb temperature (room temp) of air and wet
bulb temperature of entering air from Humidity chart.
Using ambient temperature of 32 Co and RH=75%
i.e.; At T dry bulb = 32 oC =305 K
T Wet bulb =28 oC =301 K
s handbook
Humidity of inlet air=H1= 0.022 kg of water/kg of dry air
Humidity of inlet air=154grain/kg of dry air
Now this air is heated by steam from 32 Co to 148 Co (dry bulb temp. of heated air) and the wet
bulb temperature of heated air is found with the help of dry bulb & humidity of heated air
entering the dryer from humidity chart.
i.e.; At T dry bulb = 421K
H1= 0.02 kg of water/kg of dry air
T Wet bulb = 318.53K
109
4-3-9 Outlet air temperature (Tb)
The proper outlet gas temperature is a matter of economics,
It is estimated from
Where
Nt = No. of transfer units
(1.5 2.5 for rotary dryers)
Ta = 421K
T Wb = 318.53K
Take Nt =1.5, putting the values in equation no.1
Air outlet temperature comes = Tb = 341.394K
Temperature of Feed
Inlet feed temperature (Tsa)
Feed enters the dryer at Tsa = 298.15 K
Outlet Feed temperature (Tsb)
Feed leaves the dryer at Tsb = 408.15 K
110
4-3-10 Temperature Pattern In dryers
Figure 4- 5 Temperature Pattern in continuous counteracting adiabatic Dryers [23]
As it is clear from figure that feed inlet temp. Should be less than gas outlet temp. and it
should also less than wet bulb temp. of air, so our selected feed inlet temperature is correct.
From the above figure it is clear that outlet temp. of solid is slightly greater than gas outlet
temp. So our selected solid outlet temperature is correct.
4-3-11 Temperatures
Table 4- 8 Inlet and Outlet Temperature of Dryer

Material Inlet Temperature Outlet
(K) Temperature (K)
Feed 298.15 408.15
Air 421 341.8447
111
4-3-12 Drum Diameter
To calculate diameter, we have to go through the following procedure
Calculate heat duty on dryer (qt)

Calculate mass flow rate of air entering (mg)
Choose the air mass velocity (G)
Find the dryer area (A)
4-3-13 Calculation of heat load on dryer (qt)
Heat must be supplied to a dryer to accomplish the following
Heat the feed (solid & liquid) to the vaporization (wet bulb) temperature.
Vaporize the liquid.
Heat the solids to their final temperature.
Heat the vapor to its final temperature.
In general, rate of heat transfer per unit mass can be calculated as follows
Where;
qt = Rate of heat transfer
ms = 97.216 kmol/hr
Tsa = 298.15 K
Tsb = 408.15 K
Ta = 421K
Tb = 341.3941
T Wb = 318.53
Xa = 0.0478= 4.78%
Xb = 0
KJ/kg (At wet bulb temp.) (Appendix 7)
112
Cps = 23.45 KJ/kmolK [At temp. = (408.15+298.15)/2]
Cpl = 80.535 KJ/kmolK [At temp. = (318.53+298.15)/2]
Cpv = 29.82 KJ/kmolK [At temp.= (341.39+318.53)/2]
Putting these values in equation above we get
qt = 461989 kJ/hr
4-3-14 Calculation for air flow rate (mg)
Mass flow rate of air entering is found from given formula
Where
Csb = 1.005 + 1.88H = Humid Heat =1.0464 kJ/kgK
H1 = Inlet humidity
Putting the values in equation above, we get
mg = 5458 kg/hr
4-3-15 Air mass velocity (G)
The allowable mass velocity of air in direct contact rotary dryer ranges from 400 to 5000 lb/Ft2
hr.
Take G = 1400 lb/Ft2 hr = 6849.985kg/m2hr
4-3-16 Area of dryer (A)
It can be found as
A= 0.797 m2
4-3-17 Drum Diameter
Diameter is calculated by equation
113
D =1.007 m
Drying diameter ranges from 1 to 3m (McCabe, Herriot, & smith), thus the computed diameter
is accepted.
4-3-18 Drum Length
To calculate length, we have to go through the following procedure
Calculate the Volumetric heat transfer coefficient (Ua)

Calculate log mean of drying gas wet bulb depression at inlet & exit end of dryer ( Tlm).
4-3-19 Calculation for Volumetric heat transfer coefficient (Ua)
The following empirical equation is used to calculate the overall heat transfer coefficient from
perry, mccabe handbook with the index n=0.67(McCormick, 1962). The k value fall in the range
3.75 to 5.25 as suggested by AICHE for SI unit.
Assuming k = 5.25
Ua =1935.715 kg/m3hrK
4-3-20 Calculate the volume of dryer (V)
Volume of dryer is found from the given formula
V= Qt / Ua Tlm
V = 4.463 m3
4-3-21 Calculation for log mean of drying gas wet bulb depression at inlet
& exit end of dryer ( Tm)
Log mean depression of Wet bulb ( Tlm) is found from given formula
114
Tlm = 53.46 K
4-3-22 Length of dryer
Length of dryer is calculated as
L = 5.603 m
4-3-23 L/D ratio
L/D = 5.6025/1.007
L/D = 5.56
L/D ratio is more efficient between 4 and 10 for industrial dryers, therefore above length and
diameter can be accepted.
4-3-24 Rotational Speed
Speed value ranges 0.1 to 0.5 m/s, assuming the peripheral speed of rotation to be 0.1m/s.
Take Peripheral Speed = 6 m/min
RPM= Peripheral speed/ Diameter
RPM = 6
The revolution of the dryer varies between 2-5 rpm. Therefore, the above value can be accepted.
4-3-25 Lifting Flights
No. of Flights
The standard no. of flights is 2 to 4 times the diameter (m)
No. of Flights = 3D
No. of Flights = 3.014 m
4-3-26 Flights Heights
The flight heights in direct rotary dryer will range from 1/12 to 1/8 the of dryer diameter.
Flight heights = 1/10D
115
Flight heights = 0.0101 m.
4-3-27 Flights depth
FD = D/8
FD = 0.125 m
4-3-28 Shape of Flights
The shape of the flights depends upon the handling characteristics of the solids. For free flowing
materials, a radial flight with a 900 lip is employed.
4-3-29 Residence Time
Use the following empirical equation for the residence time (in minutes) in dryers are
rec
B = 5dp-0.5
B = (130)-0.5 = 0.439
= 3min
Residence time for the rotary dryer typically ranges at 5-90 min (copper, Penney, Perry, wales,
2005).
4-3-30 Outlet Humidity
The air outlet humidity is found from given formula
Where
H2 = Outlet Humidity
H1 = Inlet Humidity
H1 = 0.022 kg of water/ kg of dry air
116
ms =11652.996 kmol/hr
mg =5457.342 kg/hr
Xa = 0.047
Xb = 0
Putting the values in above equation, we get
H2 = 0.124 Kg of water/Kg of dry air[23]
117
4-3-31 Specification Sheet
Table 4- 9 Dryer Specification Sheet

Equipment Dryer
Function To reduce the Water contents
Operation Continuous
Type Indirect heated Rotary dryer
Design Data
Flow rate of Solid entering 97.224 kmol/hr
Inlet moisture content 4.7%
Outlet moisture content 0%
Mass flow rate of Air 5457.342 kg/hr
Total heat requirement 461988.5 kJ/hr
Air mass velocity 6849.985 kg/m2hr
Area of dryer 0.79674 m2
Diameter of dryer 1.007 m
Length of dryer 5.6025 m
Volume of dryer 4.46 m3
L/D ratio 5.56
Residence Time 3 min
Material of Construction Stainless steel
Utilities Steam
118
Temperatures
Material Inlet Outlet Temperature (K)
Temperature (K)
CTA 298.15 408.15
Air 421 341.8
119
4-4 CRYSTALLIZER DESIGN
4-4-1 Selection of Crystallizer
Crystallization equipment can be classified by the method used to obtain super-saturation of

the solution or slurry. Super-saturation can be obtained by cooling or evaporation of the
solution or liquor. There are four basic types of crystallizer which are described briefly below.
1) Tank Crystallizer
2) Scraped-Surface Cooled Crystallizer
3) Circulating Magma or Forced Circulation Crystallizer
4) Circulating Liquor Crystallizer
4-4-2 Tank Crystallizer
This is the simplest type of industrial crystallizing equipment. Crystallization is induced by

cooling the mother liquor in the tank which maybe agitated and equipped with coils or jackets.
Tank crystallizers are operated batch-wise, and are generally used for small-scale production.
4-4-3 Scraped-Surface Cooled Crystallizer
This typed is similar in principle to the tank type, but the cooling surfaces are continuously
scraped or agitated to prevent fouling by deposited crystals and to promote heat transfer. They
are suitable for processing high viscosity liquor. Scraped surface crystallizers can be operated
batch-wise, with recirculation of the mother liquor, or continuously. A disadvantage of this
type is that they tend to produce very small crystals. A typical unit is Swenson-Walker
crystallizer.
4-4-4 Forced Circulation Crystallizer
In this type, both the liquor and growing crystals are circulated through the zone in this zone
in which super-saturation occurs. Circulating magma are probably the most important type of
large scale crystallizers used in the chemical process industry. Designs are available in which
super-saturation is achieved by direct cooling, evaporation or evaporative cooling under
vacuum.
120
4-4-5 Circulating Liquor Crystallizer
In this type only the liquor is circulated through the heating or cooling equipment, the crystals
are retained in suspension in the crystallizing zone by the up flow of liquor. Circulating liquor
crystallizer produce crystals of regular size. The basic design consists of three components; a
vessel in which the crystals are suspended and grow and are removed, a means of producing
super-saturation and mea
design for this type of crystallizing equipment. Circulating liquor crystallizers are used for the
large scale production of a wide range of crystal products.
4-4-6 Pre-Requisites
According to our operation some of the pre-requisites or requirements are as listed below
Continuous operation
Super-saturation must be obtained by cooling
Processing of organic material
Prevention of foul prevention
4-4-7 Comparison & Selection of Crystallization
Table 4- 10 Crystallizer comparison

Crystallizer Type Application Typical Uses
Tank Batch operation, small scale Fatty acids, Vegetable oil,

production sugar
Scraped surface Organic compounds, where Chlorobenzenes, organic

fouling is a problem, viscous acids, Paraffin waxes,
material naphthalene, Urea
Forced Circulation Production of large sized Ammonia and other
crystals inorganic salts, sodium and
potassium chlorides
Circulating liquor Production of uniform Gypsum, inorganic salts,
crystals. High throughputs sodium and potassium
nitrates, silver nitrates
On the basis of the requirements and the table the crystallizer selected is the scraped surface
Swenson walker crystallizer. Its pros and cons are listed below.
121
4-4-7-1 Advantages
Less expensive type of crystallizer

Large range of volume available
High rate recirculation reduces particle deposition on walls
4-4-7-2 Disadvantage
Crystal size is difficult to control
4-4-8 Design Calculations

4-4-8-1 Design Procedure
Following are the design procedure for a Crystallizer
Selection of Crystallizer that best meets the requirement

Make a Table of Properties like Temperature, Pressure, Specific Heats, Density,
Solubility Data etc. for streams related to Crystallizer equipment
Make a Material Balance, Energy Balance and Flow sheet
Decide a Retention time
Size the Crystallizer body respective of the controlling volume required for crystal
Retention with due consideration of Minimum cross-section required for vapors
Size the Heat exchanger required for continuous cooling of the feed stream
Select the Material of Construction
122
4-4-8-2 Properties
Listed below are the tables that shows the properties of the magma stream.
Table 4- 11 Properties of magma

Components Molar Mass Heat Density Thermal Viscosity
masses fractions Capacity (kg/m3) Conductivity (Pa.s)
(J/kg oC) (W/moC)
TPA 166.13 0.1362 1201.5 1590 0.654 0.00402
4-CBA 150.13 0.0001 1201.5 1265
p-toulic acid 136.150 0.01228 1241.3 1060
Water 18.02 0.85132 4189.8 870 0.1534 0.000451
Total mass flow rate = 57116.281 kg/hr
Magma Density = 1001.135 kg/m3
Temperature at Inlet (After flashing) = 100 oC
Pressure = 1 atm = 1.01 bar
4-4-8-3 Solubility:
Solubility(kg/kg of solvent)
10
Solubility (Kg/Kg of solvent)
9
8
7
6
5
4
3
2
1
0
0 50 100 150 200 250 300
Temperature (oC)
Figure 4- 6 Solubility trend of TPA in Water
123
4-4-8-4 Assumptions
The value of residence time and crystal size are taken from literature which are as follows;
Mean crystal size = = 130 micrometer
Sizing
Vessel Sizing
Magma Density = = 1001.135 kg/m3
Total Mass Flow rate of magma = m = 57116.281 kg/hr
Volumetric flow rate = q = = 57.052 m3/hr
Volume of Crystallizer vessel = q = 28.526 m3
Volume of Crystallizer vessel with 30% safety allowance = Vv = 31.378 m3
Volume of crystallizer vessel is given by;
And height of crystallizer is
Where,
D = Dia of vessel of crystallizer
H = Height of crystallizer vessel
V = Volume of Crystallizer
Hence, from the volume equation rearrangement,
D = 2.986 m
124
Cone Volume
Sizing of Cone at the bottom of the crystallizer is necessary, so;
Volume of cone is given by;
Vc = 6.0381 m3
Angle of Repose
Angle of Repose for Terephthalic acid is 40o. Hence the angle of Cone should be around 35o
i.e less than angle of repose.
Height of Cone
Height of cone is given by;
H = Tan
Hc = 0.94 m
Total Volume of Crystallizer
Total volume of Crystallizer is given by;
V = 44.219 m3
Total height of Crystallizer
Total height of crystallizer is given by;
H = 5.42 m[24]
6-4-8-5 Heat transfer Calculations
From energy balance
Q = 15479229.66 kJ/hr or 4299786.016 J/sec
125
Cooling water mass flowrate is
mw = 130811.987 kg/hr
Initial and final Temperatures of streams
Table 4- 12 Temperature differences

Temperature (oC) Magma Water
Initial T1 = 100 t1 = 25
Final T2 = 25 t2 = 90
Temperature Differences T1 = T1 - t1 T2 = t2 - T2
75 65
Hence, Log Mean Temperature Difference or LMTD is
lm = 69.88 oC
Also, average overall heat transfer coefficient for this specific problem is taken from Plant
Design and Economics by Peter and Timmershaus.
Uc = 1200 W/ m2 oC
Heat of Crystallization is
Qc = 0.121 kJ/kg
Mass flowrate of TPA crystals
2.807 kg/sec
Hence,
Qc = 339.663 kJ/hr
Overall Heat transfer equation is
Or,
126
So, area of heat transfer has a value of
A = 51 m2
Tube Side
Inside Dia (Di) = 0.00848 m[16]
Outside Dia (Do) = 0.01702 m
Thickness of tube = 0.00202 m
Length of Tube = L = 6.1 m[17]
L/D ratio of Tube = 719
Surface Area of One Tube = At =
At = 0.326 m2
Number of Tubes = Nt =
Nt = 157
Flow area of Tube = at = 0.0293 m
Mass velocity = = 541.41 kg/m2 s
Reynolds Number = NRe =
NRe = 4069.306
Tube Film Coefficient[18] = hi =
hi = 2267.41 W/m2 oC
Shell Side
I have selected the arrangement of Tubes as triangular. So,
Tube pitch= Pt = 1.25(Do)
127
Tube pitch = 0.0213 m
Dia of Tube bundle[17] = Db =
K1 = 0.319, n1 = 2.142
Db = 0.308 m
Dia of Shell = Ds = Db
Ds = 0.400 m
Equivalent Dia = De =
De = 0.0123
Flow area of Shell = As = (Baffle Spacing = Ds/4)
As = 0.00479 m2
Mass Velocity = 1536.97 kg/m2 s
Reynolds number = NRe
NRe = 41833.22
jH = 100
ho[18] =
ho = 7588.28 W/m2 oC
Dirt factors for inner and outer Film Coefficient
hid = 0.0003 m2 oC/W
hod = 0.0001 m2 oC/W
Kw for Stainless Steel = 16 W/ m oC
128
Hence,
Ud = 481 W/m2 oC
This is value is in range as checked from the referenced book.
4-4-8-6 Evaporation rate
The evaporation of a solvent is given by the equation[25]
Where;
E = Evaporation of solvent (Mass of solvent evaporated/ Mass of solvent initially

present)
R = Ratio of molar masses of hydrated solute and anhydrous solute
C1 = Initial Concentration (at initial temperature)
C2 = Final Concentration (Taken from solubility vs temperature data of solute in

solvent)
Cp = Heat capacity of solution or magma
T1 = Initial temperature of solution
T2 = Initial temperature of solution
q = Heat of crystallization
= Heat of vaporization of solvent
For the problem at hand, the values are as follows;
R = Molar mass of Hydrated TPA/ Molar mass of anhydrous TPA
R = 1.10845, q = 0.121 kJ/kg, C1 = 0.21926 kg of TPA/ kg of solvent,
C2 = 0.0019 kg of TPA/ kg of solvent, T1 = 100 oC, T2 = 25 oC,
129
Cp = 3.61 kJ/kgoC, = 2349.5 kJ/kg
Evaporation rate is
E = 0.14068 kg of Water evaporated/ Kg of water initially present
Mass of water initially present is
46089.450 kg/hr
Hence
E = 6483.869 kg/hr
4-4-8-7 Maximum Vapor Velocity
Where ever there is considerable evaporation of liquid, the maximum vapor velocity is an
important parameter to calculate as it can affect the design of such vessel. It is given by souders-
brown equation[17] and it is written as follows
Where;
u = maximum vapor velocity
C = a proportionality constant with different values for different equipments
= density of vapors
= density of liquid
For this problem, the values are
C = 0.0244 m/sec (from literature), = 982 kg/m3, = 0.66076 kg/m3
Maximum vapor velocity is
u = 0.940 m/sec
130
4-4-8-8 Yield of Crystallization
Yield of crystallization is given by the formula[25]
W = Initial amount of mother liquor
So, Yield is
Y = 11120.537 Kg of crystals
131
Table 4- 13 Crystallizer Specification Sheet

4-4-9 SPECIFICATION SHEET
IDENTIFICATION
Name of Equiment Crystallizer
Equiment code CR-202
Number Required 1
Function To Crystallize Terephthalic acid from a
saturated Terephthalic acid solution via cooling
Operation Continuous
Type Swenson-Walker surface cooled crystallizer
Materials Handled Terephthalic acid, P-toulic acid, Water
DESIGN DATA
Operating Pressure 1 atm
Temperature 25 oC
Residence time 0.5 hour
Density 1001.14 kg/m3
VESSEL DESIGN
Height 5.8 m
Volume 37.42 m3
Diameter 2.986 m
COOLING SYSTEM DESIGN
Heat exchanger type Shell and tube Heat exchanger
Shell side Tube side
Fluid Handled Water Fluid Handled TPA solution
Mass flowrate 130811.987 kg/hr Mass flowrate 57116.28067 kg/hr
Temperature 25 to 90oC Temperature 100 to 25oC
Heat Transfer area 51 m2
Heat Duty 15479229.66 kJ/hr
Other Parameters
Evaporation rate 6484 kg/hr
Yield of Crystals 11120.537 kg of crystals
Maximum vapor velocity 0.94 m/sec
132
CHAPTER 5
Cost Estimation
5 Cost Estimation
5-1 Cost Estimation of Reactor:
Purchased cost = Bare cost from figure time base (2004) material factor pressure factor
Diameter = 4.321 m
Vessel height = 12.963 m
For
Material factor = 2
Pressure factor = 1
Purchased cost in (2004) = $252000
Index in (2018) = 536.4
Index in 2019 is 4.6% higher than 2018 = 536.4 0.046
Index in 2019 is 4.6% higher than 2018 =24.67
Index in 2019 = 536.4 + 24.67
Index in 2019 = 561.07
Cost of reactor in 2019 = original cost (index in 2018/index in 2004)
Cost of reactor in 2019 = $318301.75
5-2 Cost Estimation of Crystallizer:
Diameter = 2.986 m
Vessel height = 5.8 m
For
Material factor = 1.7
Pressure factor = 1
134
Index in 2018 = 536.4
Index in 2019 is 4.6% higher than 2018 = 24.67
Cost of crystallizer in 2019 = original cost (index in 2019/1ndex in 2004)
Cost of crystallizer in 2019 = $101048.1
5-3 Cost Estimation of Heat Exchanger:
Area = 32 m2
For carbon steel
Material factor = 1
Pressure factor = 1
Index in 2018 = 536.4
Index in 2019 = 536.4 + 24.67
Index in 2019 = 561.07
Present cost = Original cost (index at present/index at original)
Original cost = $13000
Index at present = 561.07
Index at original = 356
Present cost of Heat Exchanger = $20486
135
5-4 Cost Estimation of Pump:
The cost of single stage centrifugal pump can be estimated from the following graph:
Purchased cost in (2004) = Bare cost from graph material factor pressure factor
Index in 2018 = 536.4
Index in 2019 = 536.4 + 24.67
Index in 2019 = 561.07
Cost of pump in 2019 = original cost (index in 2019/index in 2004)
Cost of pump in 2019 = $10395
5-5 Cost Estimation of Cooler:
Diameter = 0.64 m
Length = 6 m
For
Material factor = 2
Pressure factor = 1
Index in 2018 = 536.4
Index in 2019 is 4.6% Higher than 2018 = 536.4 0.046
Index in 2019 is 4.6% Higher than 2018 = 24.67
Index in 2019 = 536.4 + 24.67
Index in 2019 = 561.07
136
Cost of centrifuge in 2019 = original cost (index in 2018/index in 2004)
Cost of centrifuge in 2019 = $30314.45
5-6 Cost Estimation of Dryer:
Cost of equipment in 2004 = $385395.97
Cost index in 2018 = $536.5
Cost index in 2004 = $395.4
According to Marshall and Swift
Present cost = $522978.5
5-7 Equipment Cost:
Table 5- 1 Equipment Cost

Name of equipment Number of Cost of 1 equipment Total cost ($)
equipment ($)
Reactor 2 318301.7 636603.5
Heat exchanger 2 20486 40972
Crystallizer 2 101048.1 202096.3
Cooler 2 30314.45 60628.9
Dryer 2 522978.5 1045975.0
Pump 8 10395 83160
Equipment cost = $2069435.8
22% of fixed capital investment = equipment cost
Hence
Fixed capital investment = Direct cost + Indirect cost
137
Direct cost
Table 5- 2 Direct Cost

Equipment cost 22% of FCI $2069435.8
Installation cost 8% of FCI $165554.8
Instrumentation cost 5% of FCI $103471.7
Piping cost 8% of FCI $165554.8
Electrical system 4.5% of FCI $93124.6
Building cost 8% of FCI $165554.8
Yard improvement 3% of FCI $62083.0
Service facility 15% 0f FCI $310415.3
Land 1.5% of FCI $31041.5
Indirect cost
Table 5- 3 Indirect Cost

Engineering and supervision 9% of FCI $186249.2
Legal expenses 7% of FCI $144860.5
Construction cost 1.5% of FCI $31041.5
Contractors fee 2.5% of FCI $51735.8
Contingency 6% of FCI $124166.1
Fixed capital investment = $3704290.0
5-8 Working Capital Investment:
15% of FCI = $310415.3
Total capital investment = fixed capital investment + working capital investment
TCI = $4014705.4
5-9 Total product cost:
Assume that FCI depreciate by straight line method for 15 years assuming 5% of salvage
value at the end of plant life
138
Depreciation = D = (v-vs)/N
V = FCI = $3704290.0
Vs = 0.05 3704290.047 = $185214.5
N = No. of years = 15
D = $234605.0
Product cost = TCI D
Product cost = $3780100.3
Fixed charges =12% of PC = $453612.0
Direction production cost = 55% of PC = $2079055.2
Plant overhead =10% of PC = $378010.0
Total manufacturing cost = Fixed charges + direct production cost + plant overhead
Total manufacturing cost = $2910677.2
5-10 Raw material cost:

20% off product cost = (0.20 3780100.38069)
20% off product cost = $756020.0
Table 5- 4 Raw Material Cost

Admin cost 5% of PC $189005.0
Distribution and selling cost 18% of PC $680418.0
Research and development cost 5% of PC $189005.0
Financing 6% of PC $226806.0
General expenses = $1285234
Total product cost = M.C. + G.E.
Total product cost = $4195911.4
139
5-11 Gross earning/income:
Wholesale price of Para-xylene per ton = $3000
Total income = selling price quantity of product manufacture
Total income = $7500000
Total income per year = 2737.5 106
Gross income = total income total product cost
Gross income = $2733304088.5
Let the tax rate is 30%
Taxes = 0.30(gross income)
Taxes =$819991226.5
Net profit = gross income taxes
Net profit = $1913312861/yr
5-12 Rate of return:
Rate of return = (net profit 100) / total investment
Rate of return = (191331281.43 100) / $4014705.4
Rate of return = 47.65%
5-13 Payback period:
Payback period = 1/ ROR
Payback period = 2.09 years[18]
140
CHAPTER 6
Process Simulation
6 Process Simulation
6-1 Introduction to Process Simulation and Aspen HYSYS
Process Simulation is a key activity in Process Engineering covering the whole life cycle of a
process, from Research & Development to Conceptual Design and Plant Operation.
HYSYS is a powerful simulation tool that has been designed to solve complex engineering
problems along with the steady state and dynamic modeling capabilities and represent a
significant progression in the engineering software industry.
The numerous components of Aspen HYSYS provide a powerful approach to steady state
modeling, mass and energy balances, equipment design, optimization and cost estimation etc.
6-2 Simulation Procedure
First open the Aspen HYSYS and opened the new window.
Then added the components in the components section.
1. Acetic Acid
2. P- Xylene
3. Cobalt Acetate (As Hypothetical Solid)
4. Manganese Acetate (As Hypothetical Solid)
5. Hydrogen Bromide Acid
Then added the fluid package in the fluid package section
o NRTL (Non-Reacting Two Liquid Model)
Then added the reaction in the reaction type section and add reaction kinetics.
Then moved towards the simulation environment.
Add a PFR to the simulation main tab.
Then added the Shell and Tube Pre-Heater H-101 and named the steams which are
added and removed from it.
Then added the parameters and conditions H-101 and calculated the results from it.
142
6-3 Simulation Results
For Simulation of H-101, Simulation Results are given below.
Figure 6- 1 Component Selection
Figure 6- 2 Fluid Package Selection
143
Figure 6- 3 Worksheet
144
CHAPTER 7
Instrumentation &
Control
7 Instrumentation and Control
7-1 Control Loops
For instrumentation and control of

control loops are most often used[26].
1) Feedback control loop

2) Feedforward control loop
3) Ratio control loop
4) Auctioneering control loop
5) Split range control loop
6) Cascade control loop
Here is given a short outline of these control schemes, so that to justify out selection of a control
loop for specified equipment.
7-2 Components of a control system
Following are the main components of a control system[26]:
7-2-1 Process
Any operation or series of operations that produce a desired final result in a process.
7-2-2 Measuring devices
As all parts of control system, measuring element is perhaps the most important. If
measurements are not made properly the remainder of the system cannot operate satisfactorily,
also the measured variable is chosen to represent the desired conditions in the process.
7-2-3 Controller
The controller is the mechanism that responds to any error detecting mechanism. The output
of the controller is predetermined function of the error.
7-2-4 Final control element
The final control element receives the signal from the controller and by some predetermined
relationship change energy input to the process.
146
7-3 Temperature Control and Measurement
This is used to control the temperature of outlet and inlet streams in heat exchanger, condenser,
heater and column, most temperature measurement in the industrial processes is made by
means of thermocouples to facilitate bringing measurements to a controlised location.
Usually where high measurement accuracy is required resistance thermometer are used. For
the control of temperature, pneumatic feedback control is used. Outlet temperature of the
system is measured, with the help of thermocouple. This temperature is fed to a comparator.
The difference between the set point and the input signal is called error, is fed to the controller,
which controls diaphragm valve to adjust the flow of hot or cooling medium[26].
7-4 Control of Pre-Heater
The control objective is to keep the exit temperature at 200 oC for our shell and tube pre heater.
The possible disturbances are:
Offset of temperature value from its desired value of 200oC.
Variation in temperature of Steam used as a heating media.
Figure 7- 1 Feedback Control loop on Shell and tube Heat Exchanger
147
CHAPTER 8
HAZOP Study
&
Enviromental Impact
Assessment
8 HAZOP STUDY & ENVIRONMENTAL IMPACT

ASSESSMENT
8-1 Hazard and Operability Study (Hazop):
A HAZOP survey is one of the most common and widely accepted methods of systematic
qualitative hazard analysis. It is used for both new or existing facilities and can be applied to a
whole plant, a production unit, or a piece of equipment It uses as its database the usual sort of
plant and process information and relies on the judgment of engineering and safety experts in
the areas with which they are most familiar. The end result is, therefore reliable in terms of
engineering and operational expectations, but it is not quantitative and may not consider the
consequences of complex sequences of human errors. The objectives of a HAZOP study can
be summarized as follows:
To identify (areas of the design that may possess a significant hazard potential.
To identify and study features of the design that influence the probability of a
hazardous incident occurring.
To familiarize the study team with the design information available.
To ensure that a systematic study is made of the areas of significant hazard potential.
To identify pertinent design information not currently available to the team.
To provide a mechanism for feedback to the client of the study team detailed
comments.
8-2 Steps Conducted In Hazop Study:
Specify the purpose, objective, and scope of the study. The purpose may be the analysis
of a yet to be built plant or a review of the risk of unexisting unit. Given the purpose
and the circumstances of the study, the objectives listed above can he made more
specific. The scope of the study is the boundaries of the physical unit, and also the range
of events and variables considered. For example, at one time HAZOP's were mainly
focused on fire and explosion endpoints, while now the scope usually includes toxic
release, offensive odor, and environmental end-points.
149
The initial establishment of purpose, objectives, and scope is very important and should
be precisely set down so that it will be clear, now and in the future, what was and was
not included in the study. These decisions need to be made by an appropriate level of
responsible management.
Select the HAZOP study team. The team leader should be skilled in HAZOP and in
interpersonal techniques to facilitate successful group interaction. As many other
experts should be included in the team to cover all aspects of design, operation, process
chemistry, and safety. The team leader should instruct the team in the HAZOP
procedure and should emphasize that the end objective of a HAZOP survey is hazard
identification; solutions to problems are a separate effort.
8-3 Study:
1) Collect data. Theodore16 has listed the following materials that are usually needed.
Process description.
Process flow sheets.
Data on the chemical, physical and toxicological properties of all raw materials,
intermediates, and products.
Piping and instrument diagrams (P&IDs).
Equipment, piping, and instrument specifications.
Process control logic diagrams.
Layout drawings.
Operating procedures.
Maintenance procedures.
Emergency response procedures.
Safety and training manuals.
150
Figure 8- 1 HAZOP Method flow Diagram[18]
151
Table 8- 1 HAZOP Guide Words and Meanings[18]

Guide Words Meaning
No Negation of design intent
Less Quantitative decrease
More Quantitative increase
Part of Qualitative decrease
As well as Qualitative Increase
Reverse Logical opposite of the intent
Other than Complete substitution
Conduct the study. Using the information collected, the unit is divided into study "nodes" and
the sequence diagrammed in Figure, is followed for each node. Nodes are points in the process
where process parameters (pressure, temperature change between nodes as a result of the
operation of various pieces of equipment' such as distillation columns, heat exchanges, or
pumps. Various forms and work sheets have been developed to help organize the node process
parameters and control logic information.
When the nodes are identified and the parameters are identified, each node is studied by
applying the specialized guide words to each parameter. These guide words and their meanings
are key elements of the HAZOP procedure. They are listed in Table (9.1).
Hazop Study
Repeated cycling through this process, which considers how and why each parameter might
vary from the intended and the consequence, is the substance of the HAZOP study.
2) Write the report. As much detail about events and their consequence as is uncovered
by the study should be recorded. Obviously, if the HAZOP identifies a not
improbable sequence of events that would result in a disaster, appropriate follow-
up action is needed. Thus, although risk reduction action is not a part of the HAZOP,
the HAZOP may trigger the need for such action.
The HAZOP studies are time consuming and expensive. Just getting the P & ID's up to date on
an older plant may be a major engineering effort.
152
Still, for processes with significant risk, they are cost effective when balanced against the
potential loss of life, property, business, and even the future of the enterprise that may result
from a major release.
Table 8- 2 HAZOP Guide Words and Meanings

Process Guide Possible Cause Possible Action required
Parameters Word Concequence
Flow No Pipe Damage Loss of Feed in Maintenance

Reactor Required
Flow Less Pipe Leakage Less Decrease in the Repairing Pipeline

Reactor
Flow More Flow Control Overflow Valve Repairing

Failure
Temperature Less Less Heating No reaction Provide External

Issue Temperature
Temperature No No Healing No Product Rise of

Temperature
Temperature More Inadequate Inappropriate Choice of Coolant

Cooling Coolant Selection
Pressure No No Need Flow No Reaction Pipeline

Maintenance
Pressure Less Feed Pipeline Reaction Disturbs/ Scheduled

Leakage No product Inspections
Pressure More Overflow Quality Distribution Scheduled

Occurs Inspections
153
ENVIRONMENTAL IMPACT ASSESSMENT
8-4 Definition
EIA is an activity designed to identify and predict the impact of a project on

biogeophysicochemical environment and on human health so as to recommend appropriate
legislative measures, programs, and operational procedures to minimize the impact.
Silent features of EIA:
Identifies the possible positive and negative impacts to the environment
Provides for a plan which will reduce or offset the negative impacts of a project
Provides a monitoring program
The proposed project is for the production of 265 tons/day production of Terephthalic acid
located at Gwadar, Baluchistan. The raw materials used for this production are para-xylene,
acetic acid, catalyst that is the combination cobalt acetate, manganese acetate salts and
hydrogen bromide as promoter. Hydrogen is used in purification section.
8-5 Exposure
The Toxicity of the product is not very high. Terephthalic acid has low order of toxicity.
The normal precautions used in handling industrial chemicals should be observed. If
ventilation is inadequate a toxic dust respirator should be used to avoid prolonged
exposure. However, the industry has other chemicals as waste (Acetic Acid, Para
Xylene etc.).
Degradation of terephthalic acid by soil bacteria was shown by multiple studies to
happen rapidly (near complete removal via several different studies within a few days)
via both aerobic and anaerobic bacterial degradation.
The half-life of terephthalic acid in aquatic media is estimated to be 1.1 years with
respect to chemical destruction via hydroxyl radicals. However, the net aquatic half-
life should be much shorter due to biodegradation[27].
154
8-6 Flammability
The flammability limits for Terephthalic acid are given below.
Table 8- 3 Flammability Limits[28]

Dust Cloud 0
Exposibility index 6.9
Ignition Index 3
Ignition Temperature 680oC
Minimum Ignition Energy 0.020J
Min. Explosive 0.05g/L
Concentration
Relative flammability Inert
By spark ignition 80
Limiting oxygen 15%
Concentration
Explosive severity 2.3
Concentration, g/L 0.1-1 g/L
Max. Pressure 324-634 Kpa
8-7 Water Hazards

The pollution by this plant is contributed by the presence of acetic acid. Acetic acid solution in
water or organic solvent can be very strongly corrosive to the skin. Any solution containing
more than half of acetic acid should be considered as corrosive acid. Its action is insidious
because there is no immediate burning sensation upon applying the strong acid on unbroken
skin and blisters appear within 30 min. washing with water or bicarbonate seldom alleviates
the pain[27].
155
8-8 Treatment
Considering all these factors the waste water from the plant should be treated properly before
letting into the water channel. Since the waste water contains organic compounds like acetic
acid and p-Xylene it is necessary to recover these organic contents and then proceed with the
treatment of the water. Water treatment procedure contains three stages. The primary method
comprises of the removal of large floatation and suspended impurities.
The equipment used are Sedimentation Tanks, etc. The secondary treatment is a step where the
process of biodegradation takes place. Here the oxygen supplied to the bacteria is consumed
under controlled condition. The idea behind it is to consume all the oxygen in the plant rather
than in the water course. The process is also known as activated sludge process. Trickling filters
are commonly used for this purpose[27].
Following steps are involved listed below:
8-8-1 Concentration:
This step involves the removal of water so that the volume is reduced as much as possible to
facilitate the efficient handling of the sludge.
8-8-2 Digestion:
This is the stage where the sludge is stabilized by digesting it under aerobic or anaerobic
conditions.
8-8-3 Conditioning:
The stabilized sludge is added with some chemicals like iron salt, alum, lime and
polyelectrolyte to improve its dewatering characteristics.
8-8-4 Dewatering:
The sludge is further processed for removal of water by mechanical means. This product from
this stage is a solid waste material.
8-8-5 Oxidation:
The sludge is oxidized to remove any un-oxidized organic matter and stabilized further.
156
8-8-6 Ultimate Sludge Disposal:
The sludge is usually disposed by spraying it on cropland where it functions as fertilizer or it

is dumped in the sea.
8-9 Human Exposure

8-9-1 Consumer Exposure
Terephthalic acid is used primarily to make polyethylene terephthalate (PET) resins and fibers.
The majority of end uses for PET are consumer applications. PET containers are used for a
wide variety of food and beverage packaging. Terephthalic acid is non-volatile, so the potential
for residual Terephthalic acid off-gassing is limited. Possible consumer exposures to
Terephthalic acid may occur through dermal contact with PET products, as a result of
consumption of food products stored in PET containers, or through the inadvertent ingestion
of PET particles or films. Although there is little information in the public domain concerning
residual Terephthalic acid in PET, the residual level is believed to be very low. This is because
the nature of the equilibrium condensation polymerization that is used to make PET requires
that residual monomer levels be very low in order to produce a high molecular weight polymer
such as those used in typical fiber and packaging applications. Theoretical calculations for a
typical PET polymer predict that the residual Terephthalic acid should be less than 10 ppm [1].
Migration of Terephthalic acid into food simulants has been found to be less than 0.2 mg/kg
food simulant even under severe test conditions (3% acetic acid, 2 hours at 100oC and HB307
synthetic triglyceride oil, 2hours at 100oC. Migration under more typical, less severe conditions
of use is expected to be significantly less. Based on this information, there is very little potential
for exposure to Terephthalic acid from consumption of food stored in PET containers or
through dermal contact[27].
8-9-2 Occupational Exposure
A small number of large producers using continuous enclosed processes, with limited
occupational exposure, manufactures Terephthalic acid as a solid or a melt. Based on data,
workers in Terephthalic acid loading and chemical operations are estimated to have potential
inhalation dose rates ranging from <0.07 to 180 mg/day. In one U.S manufacturing site, the air
concentrations of Terephthalic acid for worker exposures were an average of 1.18 mg/m3
(range 0.006 to 13.59 mg/m3).These exposures do not take into account the use of respiratory
protection.
157
If respirators are used, and appropriately selected, used and maintained in accordance with an
acceptable respiratory protection program, dose rates would be less than 30 mg/day[27].
8-10 Environmental Precautions of Para Xylene

Prevent runoff and contact with waterways, drains or sewers. If large amounts have been
spilled, inform the relevant authorities.[29]
Atmosphere release: Use water spray to disperse the vapors.

Soil release: Collect liquid in an appropriate container or absorb with an inert material.
Underwater release: Do not flush to severe.
8-11 Accidental Release Measures for Acetic Acid

Following are the accidental release measures for acetic acid[30];
Environmental Precautions:
Prevent further leakage or spillage if safe to do so. Do not contaminate water. Avoid discharge
into drains, water courses or onto the ground. In case of large spill, dike if needed.
Methods for Containment:
Remove all sources of ignition. Stop the flow of material, if this is without risk. Prevent entry
into waterways, sewer, basements or confined areas. Dike the spilled material, where this is
possible.
Methods for Cleaning Up:
Use spark-proof tools and explosion-proof equipment. All equipment used when handling the
product must be grounded. Absorb spill with an inert material (e.g. vermiculite, dry sand, earth,
cloth, and fleece) and place in a suitable non-combustible container for reclamation or disposal.
Do not use combustible materials, such as sawdust. Clean contaminated surface thoroughly.
Neutralize spill area and washings with soda ash or lime. Never return spills in original
containers for re-use. Clean up in accordance with all applicable regulations[31].
158
Appendix
159
9 APPENDIX
Tables
Table 9- 1 Viscosity of Gases[16]
160
Table 9- 2 Viscosity of Liquids[16]
161
Table 9- 3 Properties of Saturated Steam[23]
162
Table 9- 4 Heat Exchanger Tube Data[16]
163
Charts
Chart 9- 1 Shell Side Heat transfer coefficient curve[16]
164
Chart 9- 2 Viscosity of Gases[16]
165
Chart 9- 3 Viscosity of Liquids[16]
166
Chart 9- 4 Humidity Charts [23]
167
Chart 9- 5 Enthalpy Entropy Diagram[23]
168
References
1. Tomás, R.A.F., J.C.M. Bordado, and J.F.P. Gomes, p-Xylene Oxidation to Terephthalic Acid:
A Literature Review Oriented toward Process Optimization and Development. Chemical
Reviews, 2013. 113(10): p. 7421-7469.
2. Wang, Q., et al., Semicontinuous Studies on the Reaction Mechanism and Kinetics for the
Liquid-Phase Oxidation of p-Xylene to Terephthalic Acid. Industrial & Engineering Chemistry
Research, 2007. 46(26): p. 8980-8992.
3. Zein, R., et al., PET Production. 2010.
4. Information, N.C.f.B. Properties of Terephthalic Acid. July 14, 2019; Available from:
https://pubchem.ncbi.nlm.nih.gov/compound/Terephthalic-acid.
5. Matthey, J. Process Description. Johnsen Matthey process Technologies 2017.
6. Wang, Q., et al., Kinetics of p-Xylene Liquid-Phase Catalytic Oxidation to Terephthalic Acid.
Industrial & Engineering Chemistry Research, 2005. 44(2): p. 261-266.
7. Moulijn, J.A., M. Makkee, and A.E. van Diepen, Chemical Process Technology. 2013: Wiley.
8. SMITH, W. and R. CHAPMAN, Chemical Process Ind: Org Chem V2: Chemical Process
Industries : Organic Chemicals and Allied Industries. 2016: CBS Publishers & Distributors.
9. Chauvel, A. and G.G. Lefebvre, Petrochemical Processes: Technical and Economic
Characteristics. 1989: Gulf Publishing Company.
10. Chauvel, A., G. Lefebvre, and N. Marshall, Petrochemical processes : technical and economic
characteristics. 1989, Paris: Technip.
11. Ullmann's Encyclopedia of Industrial Chemistry. 2003: John Wiley & Sons.
12. Othmer, K., Kirk-Othmer Encyclopedia of Chemical Technology. 2005: Wiley.
13. Weissermel, K., et al., Industrial Organic Chemistry. 2003: Wiley-VCH.
14. Wiley-VCH, Ullmann's Encyclopedia of Industrial Chemistry. 2003: John Wiley & Sons.
15. Chemicals, L., Annual Report, Lotte Chemicals. 2018.
16. Kern, D.Q., Process Heat Transfer. 1997: Tate McGraw-Hill Publishing Company.
17. Coulson, J.M., et al., Coulson & Richardson's Chemical Engineering. 1999: Butterworth-
Heinemann.
18. Peters, M.S., K.D. Timmerhaus, and R.E. West, Plant Design and Economics for Chemical
Engineers. 2003: McGraw-Hill Education.
19. Silla, H., Chemical Process Engineering: Design And Economics. 2003: CRC Press.
20. Moulijn, J.A., M. Makkee, and A. van Diepen, Chemical process technology. 2001: John Wiley
& Sons.
21. Levenspiel, O., Chemical reaction engineering. 1972: Wiley.
22. M. Dostál, K.P., F. Rieger, Measurement of Heat Transfer Coe cients in an Agitated
Vesselwith Tube Baffles. 2010.
23. McCabe, W.L. and J.C. Smith, Unit operations of chemical engineering. 1967: McGraw-Hill.
24. Myerson, A., Handbook of Industrial Crystallization. 2002: Elsevier Science.
25. Coulson, J.M., et al., Coulson & Richardson's Chemical Engineering: Particle technology and
separation processes. 5th ed. 1996: Butterworth-Heinemann.
26. Coughanowr, D.R., Process system analysis and control. Vol. 3rd Edition.
27. Terephthalic Acid Report Available from: http://www.inchem.org/documents/sids/sids/100-
21-0.pdf.
28. Publications, U., Material Safety Data Sheet of Terephthalic Acid. 2001.
29. cdhfinechemicals, Material Safety Data Sheet of p-Xylene.
30. Forensics, P., Material Safety Data Sheet of Acetic Acid. 2012.
31. EPA, U. SIDS Initial Assessment Report. Available from:
http://www.inchem.org/documents/sids/sids/100-21-0.pdf.
169

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265 MTPD Production of

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DEPARTMENT OF CHEMICAL ENGINEERING

MUHAMMAD NAWAZ SHARIF UNIVERSITY OF

DEPARTMENT OF CHEMICAL ENGINEERING

Dr. Waqas Aleem

PROJECT GROUP MEMBERS

Akasha Noor 2015-CH-708

Muhammad Bilal 2015-CH-709

Muhammad Ali 2015-CH-717

Rashail Ashas 2015-CH-718

DEPARTMENT OF CHEMICAL ENGINEERING

This Project Report is submitted to the Department of Chemical

Name Dr. Waqas Aleem

Head of Department/Project Incharge

Name Dr. Asim Umer

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

DEPARTMENT OF CHEMICAL ENGINEERING

Name Registration No. Signature

Akasha Noor 2015-CH-708

Muhammad Bilal 2015-CH-709

Muhammad Ali 2015-CH-717

Rashail Ashas 2015-CH-718

DEPARTMENT OF CHEMICAL ENGINEERING

Figure 1- 2 PTA capacity- pacific Asian 2016 ____________________________________ 29

Figure 1- 3 Global productions 2014 ___________________________________________ 29

Figure 1- 4 Global exports 2016 _______________________________________________ 30

Figure 1- 5 Global consumption 2015 __________________________________________ 30

Figure 2- 1 Importance of PET & TPA 35

Figure 2- 2 Reaction Scheme _________________________________________________ 37

Figure 2- 3 Hydrolysis Reaction _______________________________________________ 40

Figure 2- 4 Global Production of PET __________________________________________ 43

Figure 2- 5 Growth rate of PET per year ________________________________________ 44

Figure 2- 6 Catalytic Isomerization of dipotassium o-phthalate_______________________ 47

Figure 2- 7 Two-step conversion to TPA reaction from dipotassium p-phthalate _________ 48

Figure 2- 8 Ammoxidation of p-xylene _________________________________________ 49

Figure 2- 9 Acid oxidation of p-xylene__________________________________________ 51

Figure 2- 10 Process Flow Diagram ___________________________________________ 54

Figure 2- 11 TPA Demand Chart ______________________________________________ 56

Figure 3- 1 FMT material balance 58

Figure 3- 2 CSTR Reactor 1 material balance ____________________________________ 59

Figure 3- 3 Condenser 1 and Gas Liquid Separator material balance __________________ 60

Figure 3- 4 Crystallizer and De-Engaging Vessel material balance ____________________ 61

Figure 3- 5 Centrifuge 1 material balance _______________________________________ 63

Figure 3- 6 Dryer 1 material balance ___________________________________________ 64

Figure 3- 7 Re-Slurry Tank and Reactor 2 material balance _________________________ 65

DEPARTMENT OF CHEMICAL ENGINEERING

Figure 3- 8 Crystallizer 2 and de-engaging tank material balance _____________________ 66

Figure 3- 9 Centrifuge 2 material balance _______________________________________ 67

Figure 3- 10 Dryer 2 material balance __________________________________________ 68

Figure 3- 11 Pre-Heater heat balance ___________________________________________ 69

Figure 3- 12 Compressor heat balance __________________________________________ 70

Figure 3- 13 Cooler heat balance ______________________________________________ 70

Figure 3- 14 Reactor heat balance _____________________________________________ 71

Figure 3- 15 condenser heat balance ____________________________________________ 72

Figure 3- 16 Crystallizer heat balance __________________________________________ 72

Figure 3- 17 Condenser heat balance ___________________________________________ 74

Figure 3- 18 Dryer heat balance _______________________________________________ 74

Figure 3- 19 Pre-Heater 2 heat balance__________________________________________ 76

Figure 3- 20 Compressor 2 heat balance_________________________________________ 76

Figure 3- 21 Reactor 2 heat balance ____________________________________________ 77

Figure 3- 22 Crystallizer 2 heat balance _________________________________________ 78