G06 Aryclic Production
Short Description
arylic production...
Description
FINAL REPORT 6 May 2009
70000 metric ton Acrylic Acid Production Plant
Prepared by: Jackson Toh Lee Sin Wei Lee Yu Wee Lim Yee Chiat Mohd Izham bin Ibrahim
KEK 050019 KEK 050035 KEK 050036 KEK 050039 KEK 050042
Department of Chemical Engineering University of Malaya 50603 Kuala Lumpur
TABLE OF CONTENT Content Chapter 1:
Pages
Introduction
1.1
Biodiesel Production
1-1
1.2
Glycerol Produced from Biodiesel Plant
1-1
1.3
Potential Product of Glycerol 1.3.1 Process Route 1.3.1.1 Acrylic Acid via Acrolein 1.3.1.2 Propylene Glycol 1.3.1.3 Hydrogen 1.3.1.4 Epichlorohydrin 1.3.2 Comparison of the Products
1.4
1-2 1-2 1-2 1-3 1-3
Introduction of Acrylic Acid 1.4.1 Description 1.4.2 Chemical Identification 1.4.3 Potential Usage of Acrylic Acid 1.4.4 Physical Properties of Acrylic Acid
1.5 References Chapter 2:
1-4 1-4 1-4 1-5 1-6
Process Description of Acrylic Acid Production
2.1
Process Principle
2-1
2.2
Unit Operation Description 2.2.1 Reactor 1, CRV-100 2.2.2 Separator, V-100 2.2.3 Reactor 2, CRV-101 2.2.4 Quenching Tower, T-100 2.2.5 Extractive Distillation Column, T-101 2.2.6 Decanter, X-100 2.2.7 Solvent Recovery Distillation Column, T-102
2-1 2-2 2-2 2-2 2-3 2-3 2-3
2.3
Process Description
2-3
2.4
Process Flow Diagram 2.4.1 Flow Description
2-6 2-7
2.5
References
2-10 i
TABLE OF CONTENT Content Chapter 3: 3.1
Plant Economic & Feasibility Study
Market Analysis 3.1.1 Global Demand 3.1.2 Local Demand 3.1.3 Forecasted Future Demand 3.1.4 Production of Acrylic Acid 3.1.5 Major Manufacturer of Acrylic Acid
3.2
3.3
3.4
3.5
Pages
3-1 3-2 3-2 3-2 3-3
Location of Acrylic Acid Plant 3.2.1 Site Selection 3.2.2 Plant location
3-3 3-5
Government Policy-Taxation 3.3.1 Company Tax 3.3.2 Real Property Gain Tax 3.3.3 Sales Tax 3.3.4 Import Tax
3-6 3-7 3-7 3-7
Economic Evaluation
3-7
3.4.1 Purchased Equipment 3.4.2 Total Capital Investment 3.4.3 Total Product Cost 3.4.4 Profitable Analysis
3-8 3-9 3-10 3-11
References
3-13
ii
TABLE OF CONTENT Content
Pages
Chapter 4: Environmental, Safety and Health 4.1
4.2
Environment 4.1.1 Law and Regulation 4.1.2 Waste Water Treatment 4.1.3. Gas Emmision and Treatment
4-1 4-1 4-3
Health 4.2.1 Effect to Human 4.2.1.1 Acetic Acid 4.2.1.1.1 Health Hazard
4-5
4.2.1.1.2. Exposure Limits
4-5
4.2.1.2 Acetol 4.2.1.2.1 Health Hazard
4-5
4.2.1.2.2 Exposure Limits
4-5
4.2.1.3 Acrolein 4.2.1.3.1 Health Hazard
4-5
4.2.1.3.2 Exposure Limits
4-6
4.2.1.4 Acrylic Acid 4.2.1.4.1 Health Hazard
4-6
4.2.1.4.2 Exposure Limits
4-6
4.2.1.5 Carbon Dioxide 4.2.1.5.1 Health Hazard
4-6
4.2.1.5.2 Exposure Limits
4-7
4.1.1.6 Glycerol 4.2.1.6.1 Health Hazard
4-7
4.2.1.6.2 Exposure Limits
4-7
iii
TABLE OF CONTENT Content
Pages
Chapter 4: Environmental, Safety and Health 4.2.2 Effect to Environment
4.3
4.2.2.1 Acetic Acid
4-7
4.2.2.2 Acrolein
4-7
4.2.2.3 Acrylic Acid
4-7
4.2.2.4 Glycerol
4-8
Safety 4.3.1 Hazard Introduction
4-8
4.3.2 Handling and Storage of Hazardous Chemical
4.4
4.3.2.1 Acetic acid
4-9
4.3.2.2 Acetol
4-9
4.3.2.3 Acrolein
4-9
4.3.2.4 Acrylic Acid
4-10
4.3.2.5 Glycerol
4-10
4.3.2.6 Isopropyl Acetate
4-10
4.3.2.7 Thermal Oil
4-11
References
4-11
iv
TABLE OF CONTENT Content
Pages
Chapter 5: Mass and Energy Balances 5.1
Introduction
5-1
5.2
Comparison between Manual Calculations and HYSIS Result 5.2.1 Approach of Manual Calculation 5.2.2 Approach to HYSIS Simulation
5-1 5-1
Mass Balance Results 5.3.1 Feed rate calculation 5.3.2 Mixture of Stream 4 and 16 5.3.3 CRV-100 5.3.4 V-100 5.3.5 Purge Stream from Stream 10 5.3.6 Mixture of Stream 14, 15 and 16 5.3.7 Mixture of Stream 20, 21 and 22 5.3.8 CRV-101 5.3.9 Mixture of Stream 26 and 34 5.3.10 T-100 5.3.11 MIX-100 5.3.12 T-101 5.3.13 X-100 5.3.14 T-103
5-1 5-2 5-2 5-2 5-3 5-4 5-4 5-4 5-5 5-5 5-5 5-6 5-6 5-7
5.3
5.4
Comparison of Mass Balance Results between Hand Calculations with HYSIS 5-7
5.5
Energy Balance Results
5.6
Comparison Energy Balance Result between Hand Calculation and HYSIS
5-8
5-9
v
TABLE OF CONTENT Content
Pages
Chapter 6: Packed Bed Reactor 1
6.1
CHEMICAL ENGINEERING DESIGN
6.1.1 Introduction
6-1
6.1.2
6-2
Type of Catalyst
6.1.3 Type of Reactor 6-2 6.1.3.1 Packed Bed Reactor 6-2 6.1.3.1.1 Type of Heat Transfer Fluid 6-3 6.1.3.1.2 Packed Bed Reactor Dimension 6-4 6.1.3.1.3 Equation Involved in Packed Bed Reactor Design 6-5 6.1.3.1.3.1 Rate Law 6-5 6.1.3.1.3.2 Mole Balance 6-6 6.1.3.1.3.3 Ergun Equation for Pressure Drop 6-6 6.1.3.1.3.4 Simultaneous Ordinary Differential Equations 6-7 6.1.3.1.4 Packed Bed Reactor Optimization 6-8 6.1.3.1.4.1 Shell Diameter Analysis 6-9 6.1.3.1.4.2 Pressure Analysis 6-10 6.1.3.1.4.3 Temperature Analysis 6-12 6.1.3.1.4.4 Result of Packed Bed Reactor Optimization Analysis 6-12 6.1.3.2 Fluidized Bed Reactor 6-13 6.1.3.2.1 Equation Involved in Fluidized Bed Reactor Design 6-14 6.1.3.2.1.1 Conversion of Glycerol in Fluidized Bed Reactor 6-14 6.1.3.2.2 Fluidized Bed Reactor Optimization 6-15 6.1.3.2.2.1 Temperature Analysis 6-15 6.1.3.2.2.2 Reactor Diameter Analysis 6-16 6.1.3.2.2.3 Result of Fluidized Bed Reactor Optimization Analysis 6-17 6.1.3.3 Comparison of Packed Bed and Fluidized Bed Reactor 6-17 6.1.4 Heat Duty of Heating Jacket
6-18
vi
TABLE OF CONTENT Content
Pages
Chapter 6: Packed Bed Reactor 1 6.1.5
Clean Overall Heat Transfer Coefficient 6.1.5.1 Tube-side Film Coefficient, hio 6.1.5.2 Shell-side Film Coefficient, ho
6-19 6-19 6-19
6.1.6
Fouling Factor
6-20
6.1.7 Summary of Specification of Reactor 1
6-21
6.2
MECHANICAL ENGINEERING DESIGN
6.2.1
Design Pressure
6-22
6.2.2
Design Temperature
6-22
6.2.3
Material of Construction
6-22
6.2.4
Design Stress
6-22
6.2.5
Welded Joint Efficiency
6-23
6.2.6
Corrosion Allowance
6-23
6.2.7
Minimum Practical Wall Thickness
6-23
6.2.8 Head and Closure
6-24
6.2.9
6-24
Connection
6.2.10 Manhole
6-24
6.2.11 Compensation for Openings
6-25 vii
TABLE OF CONTENT Content
Pages
Chapter 6: Packed Bed Reactor 1 6.2.11.1 Compensate Opening for Feed 6.2.11.2 Compensate Opening for Molten Salt (Heater)
6-25 6-25
6.2.12 Dead Weight Load 6.2.12.1 Cylindrical Vessel 6.2.12.2 Tubes 6.2.12.3 Catalyst 6.2.12.4 Baffles 6.2.12.5 Feed 6.2.12.6 Molten Salt 6.2.12.7 Insulation 6.2.12.8 Total Dead Weight
6-26 6-26 6-27 6-27 6-27 6-28 6-28 6-28 6-29
6.2.13 Winds Load
6-29
6.2.14 Analysis Stress 6.2.14.1 Pressure Stress 6.2.14.2 Dead Weight Stress 6.2.14.3 Bending Stress 6.2.14.4 Resultant Longitudinal Stresses
6-29 6-29 6-30 6-30 6-30
6.2.15 Vessel Support 6.2.15.1 Skirt Supports 6.2.15.2 Total Weight 6.2.15.3 Bending Stress 6.2.15.4 Dead Weight Stress 6.2.15.5 Tensile Stress 6.2.15.6 Compressive Stress
6-31 6-31 6-31 6-31 6-32 6-32 6-32
6.2.16 Criteria for Design
6-32
6.2.17 Summary of Mechanical Design of Reactor 1
6-33
viii
TABLE OF CONTENT Content
Pages
Chapter 6: Packed Bed Reactor 1
6.3
SAFETY AND PROCESS CONTROL
6.3.1
Safety Consideration 6.3.1.1 Safety Review 6.3.1.2 Reactor Potential Hazards 6.3.1.3 Reactor Safety Practices
6-36 6-36 6-37 6-37
6.3.2
Hazard and Operability Studies (HAZOP) Analysis 6.3.2.1 Objectives of HAZOP 6.3.2.2 HAZOP Procedures
6-38 6-38 6-38
6.3.3
Process Control and Instrumentation 6.3.3.1 Description of Instruments 6.3.3.2 Description of Control System 6.3.3.2.1 Inlet Feed Temperature Control 6.3.3.2.2 Inlet Feed Flow and Pressure Control 6.3.3.2.3 Molten Salt (Heating Stream) Temperature Control
6-45 6-45 6-45 6-45 6-48 6-48
6.4
Reference
6-48
ix
TABLE OF CONTENT Content
Pages
Chapter 7: Packed Bed Reactor 2
7.1.0. CHEMICAL ENGINEERING DESIGN 7.1.0.1． Vapour Phase Oxidation of Propylene and Acrolein 7.1.0.2． Objective 7.1.0.3． Reactor Selection
7-1 7-1 7-1
7.1.1. Process Description 7.1.1.1. Feed Stream Condition 7.1.1.2. Properties of Feed Stream and Cooling Stream 7.1.1.3. Properties of Catalyst
7-2 7-2 7-3
7.1.2. Process Principle 7.1.2.1. Proposed Reaction Scheme for Oxidation of Acrylic Acid
7-4
7.1.3. Chemical Design 7.1.3.1. Kinetic Parameter 7.1.3.2. Assumptions 7.1.3.3. Catalyst Weight and Pressure Drop 7.1.3.4. Reactor Sizes 7.1.3.5. Tube Size Selection 7.1.3.6. Number of Tubes 7.1.3.7. Number of Tubes Passes 7.1.3.8. Tube Pitch and Buddle Diameter 7.1.3.9. Shell Inside Diameter 7.1.3.10. Baffles
7-4 7-5 7-5 7-7 7-7 7-7 7-8 7-8 7-8 7-8
7.1.4. Cooling Stream Requirement 7.1.4.1.Log Mean Temperature Difference 7.1.4.2.Cooling Water Flow 7.1.4.3.Tube Side Heat Transfer Coefficient 7.1.4.4.Shell Side Heat Transfer Coefficient 7.1.4.5.Overall Heat Transfer Coefficient 7.1.4.6.Heat Transfer Area Required
7-9 7-9 7-10 7-10 7-11 7-12
x
Content
Pages
Chapter 7: Packed Bed Reactor 2
7.1.5. Pressure Drop 7.1.5.1. Tube Side Pressure Drop 7.1.5.2. Shell Side Pressure Drop
7-12 7-12
7.1.6. Fluidized Bed Reactor 7.6.1.1.Minimum Fluidization Superficial Velocity, vsfm 7.6.1.2.Minimum Bubbling Velocity, vmb 7.6.1.3.Terminal Velocity, ut 7.6.1.4.Superficial velocity, vsf 7.6.1.5.Actual Velocity, v 7.6.1.6.Diameter of reactor, D 7.6.1.7.Minimum Reactor Wall Thickness, tm 7.6.1.8.Outer Diameter, OD 7.6.1.9.Bubble Velocity, vB 7.6.1.10. Slugging Problem & Reactor Height at Minimum Fluidization, Hmf 7.6.1.11. Reactor Height 7.6.1.12. Pressure Drop 7.6.1.13. Comparison between FBR and PBR
7-13 7-13 7-14 7-14 7-14 7-14 7-15 7-15 7-15 7-16 7-16 7-17 7-18
7.1.7. Summary of Chemical Engineering Design
7-19
7.1.8. Cost Analysis
7-20
7.1.9. Comparison of the Conversion
7-20
7.1.10. Comparison of the Molar Flow of the Components in Reactor Product Stream 7-21 7.1.11. Case study 7.1.11.1. Optimization of Temperature 7.1.11.2. Optimization of Pressure 7.1.11.3. Summary Optimization Analysis
7-22 7-22 7-23
xi
Content
Pages
Chapter 7: Packed Bed Reactor 2
7.2.0. MECHANICAL ENGINEERING DESIGN 7.2.0.1. Codes and Standards 7.2.1. General Design Considerations 7.2.1.1. Design Pressure 7.2.1.2. Design Temperature 7.2.1.3. Material of Construction 7.2.1.4. Design Stress (Nominal Design Strength) 7.2.1.5.Welded Joint Efficiency and Construction Categories 7.2.1.6.Corrosion Allowance
7-24
7-24 7-24 7-25 7-25 7-26 7-26
7.2.2. Shell and Tube Wall Thickness Design 7.2.2.1.Shell Wall Thickness and Outer Diameter 7.2.2.2.Tube Wall Thickness 7.2.2.3.Head and Closure 7.2.2.4.Tube Sheet Thickness
7-26 7-27 7-27 7-27
7.2.3. Design Loads 7.2.3.1.Dead Weight Load 7.2.3.2.Weight of Vessel 7.2.3.3. Total Dead Weight 7.2.3.4. Wind Load
7-28 7-28 7-30 7-30
7.2.4. Stress Analysis
7-31
7.2.5. Vessel Support 7.2.5.1.Design of Skirt Support 7.2.5.2.Pipe Sizing for Nozzles and Flanges 7.2.5.3.Manholes 7.2.5.4.Base Ring and Anchor Bolt
7-32 7-33 7-34 7-35
7.2.6. Summary of Mechanical Engineering Design
7-36
xii
Content
Pages
Chapter 7: Packed Bed Reactor 2
7.3.0. SAFETY, CONTROL AND INSTRUMENTATION 7.3.1. The Importance of Safety 7.3.1.1. Safety Considerations 7.3.1.1.1. Pressure Relief Systems 7.3.1.1.2. Effects of Fouling 7.3.1.1.3. Corrosion Failure 7.3.1.1.4. Stress Failure
7-38 7-39 7-39 7-39 7-39
7.3.2. Process Safety Design
7-40
7.3.3. Process Hazard Analysis (HAZOP Analysis)
7-40
7.3.4. The Importance of Control System
7-46
7.3.4.1. Types of Controller 7.3.4.1.1. Temperature Control 7.3.4.1.2. Pressure Control 7.3.4.1.3. Level Control 7.3.4.1.4. Feed Flow Control 7.3.4.1.5. Feed Composition Control 7.3.4.2. Control System Loop 7.3.4.2.1. Feed Flow Control (Control System Loop 1) 7.3.4.2.2. Reactor Pressure Control (Control System Loop 2) 7.3.4.2.3. Cooling Stream and Reactor Temperature Control (Control System Loop 3)
7-46 7-47 7-47 7-47 7-47
7-48 7-48 7-48
xiii
TABLE OF CONTENT Content
Pages
Chapter 8: Quenching Tower
8.1
CHEMICAL ENGINEERING DESIGN
8.1.1 Objective
8-1
8.1.2
Introduction 8.1.2.1 The Mechanism of Absorption
8-1 8-1
8.1.3
General Design Decisions
8.1.4
8.1.3.1 Choices of Solvent
8-3
8.1.3.2 Determination of Operating Pressure and Temperature
8-3
8.1.3.3 Selection of the Type of Quenching Tower
8-4
8.1.3.4 Simulation of Design Problem
8-4
8.1.3.5 Physical Properties Data
8-5
8.1.3.6 Prediction of Overall Column Efficiency
8-6
8.1.3.7 Number of Stage
8-7
Plate Specifications and Configurations 8.1.4.1 Plate Contactors
8-8
8.1.4.2 Choice of Plate Type
8-9
8.1.4.3 Plate Design Algorithm
8-10
8.1.4.4 Physical Properties
8-12
8.1.4.5 Plate Spacing
8-12
8.1.4.6 Column Diameter
8-13
8.1.4.7 Flow Arrangements
8-14
8.1.4.8 Provisional Plate Design
8-15
8.1.4.9 Weep Point
8-17
8.1.4.10 Pressure Drop
8-19
8.1.4.10.1 Column Pressure Drop Estimation
8-20 xiv
TABLE OF CONTENT Content
Pages
Chapter 8: Quenching Tower 8.1.4.10.2 Dry Plate Drop
8-20
8.1.4.10.3 Residual Head
8-22
8.1.4.11 Downcomer Liquid Back-up
8-22
8.1.4.12 Residence Time
8-24
8.1.4.13 Entrainment
8-24
8.1.4.14 Trial Layout
8-25
8.1.4.14.1 Perforated Area
8-26
8.1.4.15 Hole Pitch
8-27
8.1.4.16 Height of Column
8-29
8.1.5
Summary of Chemical Design Parameter
8-30
8.2
MECHANICAL ENGINEERING DESIGN
8.2.1
Introduction
8-31
8.2.2
Vessel Function
8-31
8.2.3
Operating Design Pressure and Temperature 8.2.3.1 Design Pressure 8.2.3.2 Design Temperature
8-31 8-31 8-31
8.2.4
Material of Construction
8-32
8.2.5
Maximum Allowable Stress Value
8-32
8.2.6
Welded Joint Efficiency
8-33
8.2.7
Corrosion Allowance
8-33
8.2.8
Design of Thin Walled Vessel
8-33
8.2.9
Torispherical Head Design
8-34
xv
TABLE OF CONTENT Content
Pages
Chapter 8: Quenching Tower 8.2.10 Design of Vessel Subject to Combined Loading Dead Weight of Vessel 8.2.10.1 8.2.10.1.1 Shell 8.2.10.1.2 Plates 8.2.10.1.3 Insulation 8.2.10.2 Wind Loading 8.2.10.3 Analysis of Stress 8.2.10.1.3.1 Pressure Stresses 8.2.10.1.3.2 Longitudinal and Circumferential Stresses due to Pressure 8.2.10.1.3.3 Dead Weight Stress 8.2.10.1.3.4 Bending Stress 8.2.10.1.3.5 Check Elastic Stability (Bucking)
8-35 8-35 8-35 8-35 8-36 8-36 8-37 8-37 8-37 8-37 8-37 8-38
8.2.11 Design of Skirt Support 8.2.11.1 Operating Weight 8.2.11.1.1 Weight of Full Liquid 8.2.11.1.2 Weight of Skirt 8.2.11.2 Thickness of Skirt
8-39 8-39 8-39 8-40 8-40
8.2.12 Opening
8-41
8.2.13 Design of Manhole
8-42
8.2.14 Design of Anchor Bolt 8.2.14.1 Design Anchor Bolt 8.2.14.2 Checking Stress in Anchor Bolt
8-43 8-43 8-44
8.2.15 Design of Base Ring 8.2.15.1 Design Base Ring 8.2.15.2 Checking Stress
8-44 8-44 8-45
8.2.16 Design Parameters
8-46
xvi
TABLE OF CONTENT Content
Pages
Chapter 8: Quenching Tower
8.3 SAFETY, CONTROL & INSTRUMENTATION 8.3.1 Safety Analysis 8.3.1.1 Introduction 8.3.1.2 Hazardous and Operability Study 8.3.1.3 Conclusion
8-48 8-48 8-48 8-49
8.3.2
Control and Instrumentation 8.3.2.1 Introduction 8.3.2.2 Control of Quenching Tower 8.3.2.3 Control Variable and Parameter
8-50 8-50 8-50 8-51
8.4
Nomenclatures
8-53
8.5
References
8-57
xvii
TABLE OF CONTENT Content
Pages
Chapter 9: Extractive Distillation Column
9.1.0. CHEMICAL ENGINEERING DESIGN 9.1.1．Introduction
9-1
9.1.2． Objective
9-1
9.1.3． Process Description
9-2
9.1.4. Selection of Column 9.1.4.1. Selection of Internal Column 9.1.4.2. Packing Selection 9.1.4.3. Random Packing selection
9-3 9-3 9-3 9-3
9.1.5
9-4 9-4 9-4 9-5 9-5 9-6 9-6 9-8 9-8 9-9 9-9
Packed Column Design 9.1.5.1. Selection of solvent 9.1.5.2. Composition and condition of feed stream, distillate and bottom 9.1.5.3. Number of theoretical stages 9.1.5.4. Optimum Feed Location 9.1.5.5. Optimum reflux ratio 9.1.5.6. Column Diameter 9.1.5.7. Height of Packed Zone 9.1.5.8. Wetting rate 9.1.5.9. Liquid Hold-up 9.1.5.10. Operating Void Space
9.2.0. MECHANICAL ENGINEERING DESIGN 9.2.1．Introduction
9-11
9.2.2． Material of Construction 9.2.2.1. Design Pressure 9.2.2.2. Design temperature 9.2.2.3. Material of construction 9.2.2.4. Material of construction 9.2.2.5. Welded joint factor 9.2.2.6. Corrosion Allowance
9-11 9-11 9-11 9-11 9-11 9-12
9.2.3． Internal Fitting 9.2.3.1. Packing support
9-12 9-12 xviii
Content
Pages
Chapter 9: Extractive Distillation Column
9.2.4
9.2.3.2. Vapor distributor 9.2.3.3. Hold down plate 9.2.3.4. Liquid distributors 9.2.3.5. Liquid redistributors 9.2.3.6. Mist eliminator (Demister) 9.2.3.7. Support ledges 9.2.3.8. Manhole
9-12 9-12 9-12 9-13 9-13 9-13 9-13
Column Design 9.2.4.1. Cylindrical Shell Thickness 9.2.4.2. Vessel Head 9.2.4.3. Vessel Height 9.2.4.4. Flange 9.2.4.5. Load Analysis 9.2.4.5.1. Dead Weight loads 9.2.4.5.2. Wind load 9.2.4.6. Stress analysis 9.2.4.7. Support 9.2.4.8. Pipe Sizing for Nozzles 9.2.4.9. Reinforcement of Openings
9-14 9-14 9-14 9-14 9-15 9-15 9-15 9-15 9-15 9-15 9-16 9-16
9.3.0. SAFETY, CONTROL AND INSTRUMENTATION 9.3.1.Introduction
9-17
9.3.2． Control
9-17
9.3.3． Safety 9.3.3.1. HAZOP analysis
9-19 9-19
xix
TABLE OF CONTENT Content
Pages
Chapter 10: Distillation Column
10.1. CHEMICAL ENGINEERING DESIGN 10.1.1. Introduction
10-1
10.1.2. Distillation Column Design 10.1.2.1. Schematic Diagram of T-102 10.1.2.2. Type of Column of T-102
10-1 10-2 10-3
10.1.3. Key Components
10-3
10.1.4. Number of Stages 10.1.4.1. Relative Volatility 10.1.4.2. Number of Stages and Operating Reflux Ratio 10.1.4.2.1. Minimum Number of Stages 10.1.4.2.2. Minimum Operating Reflux Ratio 10.1.4.3. Number of Theoretical Stages 10.1.4.4. Overall Column Efficiency 10.1.4.5. Actual Number of Stages
10-3 10-3 10-4 10-4 10-4 10-5 10-6 10-7
10.1.5. Feed Point Location
10-7
10.1.6. Plate Specification 10.1.6.1. Plate Spacing 10.1.6.2. Types of Plate 10.1.6.3. Liquid and Vapour Flow in a Plate Colum
10-7 10-7 10-8 10-8
10.1.7. Plate Design Procedure 10.1.7.1. Vapour and Liquid Flow Rates 10.1.7.2. Physical Properties 10.1.7.3. Column Diameter 10.1.7.3.1. Liquid Vapour Flow Factor 10.1.7.3.2. Flooding Velocity 10.1.7.3.3. Maximum Velocity Flow Rate 10.1.7.4. Liquid Flow Pattern
10-9 10-10 10-11 10-11 10-11 10-12 10-12 10-13 xx
TABLE OF CONTENT Content
Pages
Chapter 10: Distillation Column 10.1.7.5. Provisional Plate Design 10.1.7.6. Check Weeping 10.1.7.6.1. Weir Liquid Crest 10.1.7.7. Plate Pressure Drop 10.1.7.7.1. Dry Plate Drop 10.1.7.7.2. Residual Head 10.1.7.7.3. Total Pressure Drop 10.1.7.8. Check Entrainment
10-14 10-14 10-15 10-16 10-16 10-17 10-17 10-17
10.1.8. Trial Layout
10-18
10.1.9. Perforated Area 10.1.9.1. Number of Holes
10-18 10-19
10.1.10. Column Height
10-19
10.1.11. Simulation by HYSYS 10.1.11.1. Approach by Manual Calculation 10.1.11.2. Approach by HYSYS
10-20 10-20 10-20
10.1 MECHANICAL ENGINEERING DESIGN 10.2.1. Introduction
10-21
10.2.2. General Design Consideration of Pressure Vessel 10.2.2.1. Design Pressure 10.2.2.2. Design Pressure 10.2.2.3. Materials of Construction 10.2.2.4. Design Stress 10.2.2.5. Welded Joint Efficiency 10.2.2.6. Corrosion Allowance
10-21 10-22 10-22 10-23 10-23 10-23 10-24
xxi
TABLE OF CONTENT Content
Pages
Chapter 10: Distillation Column 10.2.3 Design Column 10.2.3.1 Wall Thickness 10.2.3.2 Design of Vessel Head 10.2.0.3.2.1 Choice of Closure 10.2.0.3.2.2 Design of Torispherical Head
10-24 10-24 10-25 10-25 10-25
10.2.4 Design of Vessel Loads 10.2.4.1 Weight Loads 10.2.4.2 Vessel Weight 10.2.4.3 Plate Weight 10.2.4.4 Cage Ladder Weight 10.2.4.5 Platform Stells Weight 10.2.4.6 Total Load Weight
10-26 10-26 10-26 10-27 10-27 10-27 10-27
10.2.5 Wind Loads 10.2.5.1 Load per Unit Length 10.2.5.2 Bending Moment at Colum Height
10-28 10-28 10-28
10.2.6 Analysis of Stress 10.2.6.1 Pressure Stress 10.2.6.2 Dead Weight Stress 10.2.6.3 Bending Stress 10.2.6.4 Principal Stress 10.2.6.5 Critical Buckling Stress
10-28 10-28 10-28 10-29 10-29 10-30
10.2.7 Vessel Support 10.2.7.1 Skirt Thickness 10.2.7.2 Bending Moment at Base of Skirt 10.2.7.3 Design Criteria
10-30 10-30 10-31 10-31
10.2.8 Manhole
10-32
10.2.9 Summary
10-33
xxii
TABLE OF CONTENT Content
Pages
Chapter 10: Distillation Column
10.3 SAFETY, CONTROL AND INSTRUMENTATION 10.3.1 Introduction 10.3.1.1 Safety 10.3.1.2 Environment Protection 10.3.1.3 Equipment Protection 10.3.1.4 Smooth Plant Operation 10.3.1.5 Product Quality 10.3.1.6 Profit 10.3.1.7 Monitoring and Diagnosis
10-35 10-35 10-35 10-36 10-36 10-36 10-36 10-36
10.3.2 Distillation Control Objective
10-37
10.3.3 Column Control 10.3.3.1 Feed Stream Control 10.3.3.2 Product Quality Control 10.3. 3.3 Top Stream Control 10.3. 3.4 Bottom Stream Control
10-38 10-39 10-39 10-39 10-40
10.3.4 Instruments Notation
10-40
10.3.5 Instrumentations 10.3.5.1 Pressure Measurements 10.3.5.2 Flow Measurements 10.3.5.3 Level Measurements 10.3.5.4 Temperature Measurements
10-41 10-41 10-41 10-41 10-41
10.3.6 Hazards and Operability Study
10-43
xxiii
LIST OF TABLES Table 1.1: Comparison the Economic for Different Products of Glycerol
1-3
Table 1.2: Physical Properties of Acrylic Acid
1-5
Table 3.1: Forecasted Global Growth of the Usage of Acrylic Acid up to Year 2011
3-2
Table 3.2: Forecasted Annual Production of Acrylic Acid up to Year 2011
3-2
Table 3.3: Major Manufacturer of Acrylic Acid
3-3
Table 3.4: Price of Acrylic Acid at Asia and USA
3-3
Table 3.5: Petrochemical Plant in Gebeng
3-6
Table 3.6: Estimation of Equipment Cost
3-8
Table 3.7: Estimation of Total Capital Investment
3-9
Table 3.8: Estimation of Total Product Cost
3-10
Table 3.9: Estimation of Payback Period
3-11
Table 4.1: Waste Water Composition
4-1
Table 4.2: Waste Water Discharge Target
4-3
Table 4.3: Gas Emission Target
4-4
Table 5.1: Molar Flow Rate at Stream 5 and its Comparison with HYSIS
5-2
Table 5.2: Molar Flow Rate of Stream 6 at CRV-100 and its Comparison with HYSIS
5-2
Table 5.3: Molar Flow Rate of Stream 10 at V-100 and its Comparison with HYSIS
5-2
Table 5.4: Molar Flow Rate of Stream 20 at V-100 and its Comparison with HYSIS
5-3
Table 5.5: Molar Flow Rate of Stream 11 of and its Comparison with HYSIS
5-3
Table 5.6: Molar Flow Rate of Stream 12 and its Comparison with HYSIS
5-3
Table 5.7: Molar Flow Rate of Stream 17 and its Comparison with HYSIS
5-4
Table 5.8: Molar Flow Rate of Stream 23 and its Comparison with HYSIS
5-4
Table 5.9: Molar Flow Rate of Stream 24 at CRV-101 and its Comparison with HYSIS
5-4
Table 5.10: Molar Flow Rate of Stream 27 and its Comparison with HYSIS
5-5
Table 5.11: Molar Flow Rate of Stream 28 at T-100 and its Comparison with HYSIS
5-5
Table 5.12: Molar Flow Rate of Stream 29 at T-100 and its Comparison with HYSIS
5-5
Table 5.13: Molar Flow Rate of Stream 31 at MIX-100 and its Comparison with HYSIS 5-5 Table 5.14: Molar Flow Rate of Stream 33 at T-101 and its Comparison with HYSIS
5-6
Table 5.15: Molar Flow Rate of Stream 32 at T-101 and its Comparison with HYSIS
5-6
LIST OF TABLES Table 5.16: Molar Flow Rate of Stream 34 at X-100 and its Comparison with HYSIS
5-6
Table 5.17: Molar Flow Rate of Stream 35 at X-100 and its Comparison with HYSIS
5-6
Table 5.18: Molar Flow Rate of Stream 36 at T-103 and its Comparison with HYSIS
5-7
Table 5.19: Molar Flow Rate of Stream 37 at T-103 and its Comparison with HYSIS
5-7
Table 5.20: Summary of Energy Balance and the Comparison
5-8
Table 6.1: Property of Catalyst
6-2
Table 6.2: Property of Hot Molten Salt (HITEC)
6-4
Table 6.3: Dimension of Packed Bed Reactor
6-4
Table 6.4: Weight of Catalyst, W, Pressure Ratio, Y, Length of Reactor, L and Ratio of Length to Diameter, L/D at Different Number of Tube per Reactor
6-10
Table 6.5: Weight of Catalyst, W, Pressure Ratio, Y, Length of Reactor, L and Ratio of Length to Diameter, L/D at Different Inlet Pressure, Po
6-11
Table 6.6: Weight of Catalyst, W, Pressure Ratio, Y, Length of Reactor, L and Ratio of Length to Diameter, L/D at Different Inlet Temperature, To
6-13
Table 6.7: Results of Packed Bed Reactor Optimization Analysis
6-13
Table 6.8: Length of Reactor, L and Ratio of Length to Diameter, L/D at Different Inlet Temperature, To
6-16
Table 6.9: Length of Reactor, L and Ratio of Length to Diameter, L/D for Different Shell Diameter, IDs
6-17
Table 6.10: Results of Packed Bed Reactor Optimization Analysis
6-17
Table 6.11: Variables to Calculate Heat Duty
6-18
Table 6.12: Variables to Tube-side Film Coefficient
6-19
Table 6.13: Variables to Shell-side Film Coefficient
6-19
Table 6.14: Variables to Calculate Fouling Factor
6-20
Table 6.15: Summary of Specification of Reactor 1
6-21
Table 6.16: Variables to Calculate Optimum Diameter in Feed Opening
6-25
Table 6.17: Variables to Calculate Optimum Diameter in Molten Salt Opening
6-26
Table 6.18: Variables to Calculate Total Weight of Shell
6-26
Table 6.19: Variables to Calculate Total Weight of Tube
6-27
LIST OF TABLES Table 6.20: Variables to Calculate Total Weight of Baffles
6-27
Table 6.21: Variables to Calculate Total Weight of Feed
6-28
Table 6.22: Variables to Calculate Total Weight of Molten Salt
6-28
Table 6.23: Variables to Calculate Total Weight of Insulation
6-29
Table 6.24: Criteria for Design
6-32
Table 6.25: Summary of Mechanical Design of Reactor 1
6-33
Table 6.26: HAZOP Analysis on Packed Bed Reactor 1 – Streamline 5
6-39
Table 6.27: HAZOP Analysis on Packed Bed Reactor 1 – Streamline 6
6-41
Table 6.28: HAZOP Analysis on Packed Bed Reactor 1 – Streamline H_1
6-42
Table 6.29: HAZOP Analysis on Packed Bed Reactor 1 – Streamline H_2
6-43
Table 6.30: Description of Instrument
6-45
Table 6.31: Description of Inlet Feed Temperature Control
6-45
Table 6.32: Description of Inlet Feed Flow and Temperature Control
6-46
Table 6.33: Description of Molten Salt Temperature Control
6-46
Table 7.1: Initial Condition of Feed Stream Reactant
7-2
Table 7.2: Properties of Feed Stream and Cooling Stream
7-3
Table 7.3: Properties of Catalyst
7-3
Table 7.4: Kinetic Parameter for Oxidation of Acrolein
7-5
Table 7.5: Determination of Catalyst Weight and Pressure Drop
7-6
Table 7.6: Determination of Reactor Sizes
7-7
Table 7.7: Properties of Pipe
7-7
Table 7.8: Specifications of Baffles
7-9
Table 7.9: Determination of Tube Side Heat Transfer Coefficient
7-10
Table 7.10: Determination of Shell Side Heat Transfer Coefficient
7-10
Table 7.11: Determination of Overall Heat Transfer Coefficient
7-11
Table 7.12: Inner Diameter of Reactor for Various
vsf vsfm
Ratios
7-15
Table 7.13: Determination of Height of Reactor
7-17
Table 7.14: Comparison between FBR and PBR
7-18
LIST OF TABLES Table 7.15: Summary of Chemical Engineering Design of Reactor
7-19
Table 7.16: Comparison of the Conversion Value with the HYSYS Simulation
7-20
Table 7.17: Comparison of the Component Molar Flow with the HYSYS Simulation
7-21
Table 7.18: Design Pressure for Tube Side and Shell Side
7-24
Table 7.19: Design Temperature for Tube Side and Shell Side
7-25
Table 7.20: Design Stress for Tube Side and Shell Side
7-25
Table 7.21: Optimum Diameter for Inlet Streams and Outlet Streams
7-34
Table 7.22: HAZOP Analysis on Feed Stream of the Reactor
7-41
Table 7.23: HAZOP Analysis on Outlet Stream of Reactor
7-43
Table 7.24: HAZOP Analysis on Cooling Water Supply of Reactor
7-44
Table 7.25: Control Variables for Packed Bed Reactor
7-50
Table 8.1: Comparison between Different Trays
8‐9
Table 8.2: Summary of Chemical Design Parameter for the Quenching Tower
8‐31
Table 8.3: Piping System
8‐43
Table 8.4: Mechanical Design Parameter for Quenching Tower
8‐47
Table 8.5: Control Variable and Parameter
8‐51
Table 9.1: Comparison between Plate Column and Packed Column
9-3
Table 9.2: Comparison between Random Packing and Structured Packing
9-3
Table 9.3: Molar Flow Rate of the Inlet Streams and Outlet Streams of Extractive Distillation
Column
9-4
Table 9.4: Operating Condition of the Inlet Streams and Outlet Streams of Extractive Distillation Column
9-4
Table 9.5: Equilibrium Data for Raffinate Phase
9-5
Table 9.6: Equilibrium Data for Extracted Phase
9-5
Table 9.7: Purify of Product with vary Reflux Ratio
9-6
Table 9.8: Extractive Distillation Column Design Summary
9-10
Table 9.9: Control System for Extractive Distillation Column
9-18
Table 9.10: HAZOP Analysis
9-19
10-2
Table 10.1: Stream Description for Distillation Column T-102
LIST OF TABLES Table 10.2: Stage Requirement at Different Reflux Ratio
10-6
Table 10.3: Vapor and Liquid Flow Rates
10-10
Table 10.4: Physical Properties
10-11
Table 10.5: Provisional Design
10-15
Table 10.6: Molar Flow Rate of Feed Stream and its Comparison with Hysys
10-21
Table 10.7: Molar flow rate of Top stream and its Comparison with Hysys
10-21
Table 10.8: Molar flow rate of Bottom Stream and its Comparison with Hysys
10-21
Table 10.9: Summary of Chemical Engineering Design
10-34
LIST OF FIGURES Figure 4.1: Schematic of Water Treatment System
4-2
Figure 4.2: Schematic of Gas Treatment System
4-3
Figure 6.1: Schematic Diagram of Reactor 1
6-1
Figure 6.2: Shell-and-tube Packed-bed Reactor with Co-current Heating
6-3
Figure 6.3: Plot of Conversion and Pressure Ratio Obtained from Matlab
6-8
Figure 6.4: Data of Conversion and Pressure Ratio Obtained from Matlab
6-9
Figure 6.5: Schematic Diagram of Fluidized Bed Reactor
6-14
Figure 6.6: Ellipsoidal Head
6-24
Figure 6.7: Schematic Diagram of Opening
6-25
Figure 6.8: Mechanical Drawing of Reactor 1
6-34
Figure 6.9: Detail A of Mechanical Drawing
6-35
Figure 6.10: Process and Instrumentation Diagram (PID) of Reactor 1
6-47
Figure 7.1: Fluidized Bed Reactor
7-13
Figure 7.2: Ratio of Length and Diameter, L/D vs. Inlet Temperature, To
7-22
Figure 7.3: Ratio of Length and Diameter, L/D vs. Inlet Pressure, Po
7-23
Figure 7.4: Control System for Packed Bed Reactor
7-49
Figure 8.1 Schematic Diagram of Quenching Tower
8-5
Figure 8.2: Absorber Column Efficiency
8-6
Figure8.3: Typical Cross Flow Plate (Sieve)
8-8
Figure 8.4: Column Operation Regimes
8-8
Figure 8.5: Plate Design Algorithm
8-11
Figure 8.6: Flooding Velocity, Sieve Plate
8-13
Figure 8.7: Selection of Liquid Flow Arrangement
8-15
Figure 8.8: Relationship between the Weir Length and Downcomer Area
8-17
Figure 8.9: Weep Point Correlation
8-20
Figure 8.10: Discharge Coefficient, Sieve Plates (Liebson et al., 1957)
8-22
Figure 8.11: Entrainment Correlation for Sieve Plates
8-26
Figure 8.12: Trial Layout of the Plate Design
8-27
Figure 8.13: Relation between Downcomer Area and Weir Length
8-28
LIST OF FIGURES Figure 8.14: Relation between Hole Area and Pitch
8-30
Figure 8.15: Torispherical Head
8-36
Figure 8.16: Analysis of Stresses
8-39
Figure 8.18: Feedback Control Loop in Quenching Tower
8-53
Figure 8.19: Ratio Control Loop in Absorbed
8-53
Figure 9.1: Flow Diagram for Extractive Distillation Column
9-2
Figure 9.2: Flooding and Pressure Drop in Packed Column
9-6
Figure 9.3: Table Constant for TETP Correlation
9-8
Figure 9.4: Flow Diagram with Controller
9-17
Figure 10.1: Schematic Diagram of Distillation Column T-102
10-2
Figure 10.2: Flow of Vapor and Liquid across Each Plate
10-9
Figure 10.3: Trial Plate Layout
10-18
Figure 10.4: Complete Process Control and Instrumentation Diagram of Distillation Column 10-43
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
CHAPTER 1: INTRODUCTION 1.1 Biodiesel Production Biodiesel can be produced from vegetable oil, animal oil/fats, tallow and waste oils. There are three basic routes for biodiesel production from oils and fats. •
Base catalyzed transesterification of the oil
•
Direct acid catalyzed transesterification of the oil
•
Conversion of the oil to its fatty acids and then to biodiesel.
Almost all biodiesel is produced by base catalyzed transesterification as it is the most economical process requiring only low temperatures and pressures and producing a 98% conversion yield.[1] The production of biodiesel by using oil and fats and shown below.
The oil or fats is reacted with alcohol under proper catalyst and condition will produce biodiesel as main product and glycerol as by product for process. For every 1 tonne of biodiesel that is manufactured, 100 kg of glycerol are produced. [2] After neutralization treatment, crude Glycerol with 80-88% purity containing water and catalyst residual can be obtained. [1]
1.2 Glycerol Produced from Biodiesel Plant In year 1999 biodiesel glycerol accounted for just 7% of the glycerol market and in year 2004 that figure had grown to 19%. This has lead to oversupply in the market and new investments in oleochemical as well as biodiesel industries are expected to make the situation worse in the next couple of years. 450 million gallons of biodiesel were produced in 2007, which left with 45 million gallons of glycerol. Considering that the National Biodiesel Board is expecting 60 new plants with a production capacity of 1.2 billion gallons of biodiesel to come online by 2010, over 100 million gallons of glycerol is expected to be produced annually.[3] Due to the overcapacity of glycerol, the price
1-1
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
decreased drastically over recent years. Hence researches have been made to develop technologies to utilize the glycerol produced from biodiesel plant.
1.3 Potential Product of Glycerol By research there are several useful products that can be manufactured by using glycerol. •
Acrylic acid via acrolein
•
Propylene glycol
•
Hydrogen
•
Epichlorohydrin
1.3.1 Process Route 1.3.1.1 Acrylic Acid via Acrolein The production of acrylic acid is by two reaction routes. Glycerol (C3H8O3) is dehydrated to form acrolein (C3H4O), which acts as an intermediate (refer to Equation 1.1). Then the acrolein is oxidized to form acrylic acid (C3H4O2). (refer to Equation 1.2).
C3 H 8O3 ⎯⎯ → C3 H 4O + 2 H 2O
(Equation 1.1)
1 C3 H 4O + O2 ⎯⎯ → C3 H 4O2 2
(Equation 1.2)
1.3.1.2 Propylene Glycol
The production of propylene glycol is by dehydration of glycerol (C3H8O3) to produce an intermediate product, acetol (C3H6O2) (refer to Equation 1.3). Then it is further hydrogenated to produce propylene glycol (C3H8O2) (refer to Equation 1.4). C3 H 8O3 ⎯⎯ → C3 H 6O2 + H 2O
(Equation 1.3)
C3 H 6O2 + H 2 ⎯⎯ → C3 H 8O2
(Equation 1.4)
1.3.1.3 Hydrogen
The production of hydrogen from glycerol is by steam reforming (refer to Equation 1.5), followed by the water-gas shift reaction (refer to Equation 1.6). The overall reaction is summarized in Equation 1.7.
1-2
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
H 2O C3 H 8O3 ⎯⎯⎯ → 3CO + 4 H 2
(Equation 1.5)
CO + H 2O ⎯⎯ → CO2 + H 2
(Equation 1.6)
C3 H 8O3 + 3H 2O ⎯⎯ → 3CO2 + 7 H 2
(Equation 1.7)
1.3.1.4 Epichlorohydrin
Dichloropropanol
is
synthesized
from
glycerol
and
hydrochloric
acid.
Dehydrochlorination of the intermediates then produces epichlorohydrin.
1.3.2 Comparison of the Products Table 1.1: Comparison the economic for different products of glycerol [4, 5, 6, 7, 8, 9, 10, 11]
Acrylic acid
PG
Hydrogen
Epichlorohydrin
Annual Global
3.75 million
1.4 million ton/
675 billions
Demand
ton/ year
year
SCF/year
3.5
4.5
4.0
5.0
1650
1800
510.5
1650
Competition from
Propylene via
Propylene
Industries
Acrolein
Oxide
Methane
Propylene
1000
1410
122
1000
1.3 million ton/year
Forecasted Average Global Growth (%) Price per ton (USD)
Raw material’s price of competitor (USD/ton)
From the table above, all the potential products are considered profitable by using glycerol as raw material without consider the capital cost. However acrylic acid is chosen to be produced based on the following criteria: •
The annual global demand of acrylic acid is the highest.
•
The forecasted annual global growth is high that is 3.5%.
•
Price of glycerol is cheaper than the current raw material, propylene.
•
Storage and handling of acrylic acid is easier compared to hydrogen.
1-3
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
•
Acrylic acid is less toxic compared to epichlorohydrin.
•
The usage of acrylic acid is more and the potential market is wide.
1.4 Introduction of Acrylic Acid 1.4.1 Description
Acrylic acid or prop-2-enoic acid is a chemical compound that can be easily polymerized. Pure acrylic acid is a clear, colorless liquid with a characteristic acrid odor. It is miscible in water, alcohols, ethers and chloroform. Acrylic acid is used as monomer for acrylate resins and forms crystalline needle in solid state.
1.4.2 Chemical Identification
Structure formula:
H 2C = CHCOOH
Chemical structure:
H H OH | | | C=C–C=O | H
IUPAC name: Propenoic acid CAS number: [79-10-7] RTECS number: AS4375000 Synonyms: Ethylenecarboxylic acid, Propene acid, Propenoic acid, Vinylformic acid
1.4.3 Potential Usage of Acrylic Acid
Acrylic acid is most often been polymerize to form acrylic acid polymer. The most common product is superabsorbent polymers (SAP) that account for 32% of the global demand for acrylic acid. SAPs are cross-linked polyarcylates with the ability to absorb and retain more than 100 times their own weight in liquid. Acrylic acid also can be used to produce detergent polymer. It can be used with zeolites or phosphates in washing powder formulation. Besides that acrylic acid is also the raw material for various acrylic ester productions.
1-4
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
1.4.4 Physical Properties of Acrylic Acid
Important physical properties of acrylic acid are summarized in Table 1.2. Table 1.2: Physical properties of acrylic acid
Properties
Data
Molecular Weight
72.06 g/mol
Specific Gravity
1.050 (20/4 oC)
Melting Point
13 oC
Boiling Point (101.3 kPa)
141 oC
Flash Point
54 oC (Cleveland open cup)
Critical Temperature
380 oC
Critical Pressure
5.06 Mpa
Viscosity (25 oC)
1.149 mPa.s
Refractive Index (25 oC)
1.4185
Solubility
> 10g/L
Dissociation Constant (25 oC)
5.5 x 10 -5
pKa
4.26
Vapor Density (air =1)
2.5
Vapor Pressure (20 oC)
0.4133 kPa
Auto-ignition Temperature
360 oC
Explosive Limit
2.4 – 8.0 vol % in air
Heat of Vaporization (101.3 kPa)
45.6 kJ/mol
Heat of Combustion
1376 kJ/mol
Heat of Melting (13 oC)
11.1 kJ/mol
Heat of neutralization
58.2 kJ/mol
Heat of polymerization
77.5 kJ/mol
1-5
KKEK 4281 Design Project Chapter 1: Introduction
Group 6 Acrylic Acid Project
1.5 References 1. http://www.esru.strath.ac.uk/EandE/Web_sites/02-03/biofuels/what_biodiesel.htm 2. http://en.wikipedia.org/wiki/Biodiesel#Production 3. Frost & Sullivan - What is the Global Market Outlook for Glycerine in 2006, 19th Oct 2008. 4. http://www.alibaba.com/trade/search?Type=&ssk=y&year=&month=&industry= &location=&keyword=&SearchText=crude+glycerine&Country=MY&srchLocat ion=&srchYearMonth=&IndexArea=product_en&CatId=0 5. http://www.dow.com/productsafety/finder/prog.htm 6. http://www.icis.com/v2/chemicals/9076442/propylene-glycol/pricing.html 7. http://www.the-innovation-group.com/ChemProfiles/Propylene%20Glycol.htm 8. http://en.wikipedia.org/wiki/Ethanol#Production 9. http://www.the-innovation-group.com/ChemProfiles/Ethanol.htm 10. http://en.wikipedia.org/wiki/Hydrogen#Applications 11. http://www.the-innovation-group.com/ChemProfiles/Hydrogen.htm
1-6
KKEK 4281 Design Project Chapter 2: Process Description
Group 6 Acrylic Acid Project
CHAPTER 2: PROCESS DESCRIPTION OF ACRYLIC ACID PRODUCTION 2.1 Process Principle The raw material used is crude glycerol obtained from biodiesel plant. The purity of crude glycerol obtained is 88% purity. [1] The production of acrylic acid from glycerol is by two process routes. First, crude glycerol (C3H8O3) is dehydrated to acrolein (C3H4O) via acetol (C3H6O2) as intermediate (refer to Equation 2.1 and Equation 2.2) under heterogeneous catalytic reaction. The reaction is endothermic.
C3 H 8O3 ⎯⎯ → C3 H 6O2 + H 2O
(Equation 2.1)
C3 H 6O2 ⎯⎯ → C3 H 4O + H 2O
(Equation 2.2)
Acrolein is then oxidized to form acrylic acid in Reactor 2 (refer to Equation 2.3) via heterogeneous catalytic reaction. The reaction is exothermic. Acetic acid will form as the major by product for the process refer to Equation 2.4)
1 C3 H 4O + O2 ⎯⎯ → C3 H 4O2 2
3 C3 H 4O + O2 ⎯⎯ → C2 H 4O2 + CO2 2
(Equation 2.3)
(Equation 2.4)
2.2 Unit Operation Description 2.2.1 Reactor 1, CRV-100
In the first reactor, crude glycerol is dehydrated to acrolein via heterogeneous catalytic endothermic reaction. The catalyst used is aluminasilicates supported silicotungstic acid which by research gives a higher conversion of glycerol and higher yield of acrolein. The temperature of the reactor is maintained at 275oC by control the temperature of the inlet air-steam stream temperature. The pressure of the reactor is set at 1 atm. Under these conditions, the conversion of glycerol is 98.3% and selectivity of acrolein is 86.2%.[2, 3] Steam and air are added into Reactor 1 along with glycerol. The mass ratio of steam to glycerol is 4 to 1 while the proportion of oxygen to the total mass is 0.07. [3] Steam is added as inert gas to control the rate of the reaction. Air which consists of oxygen and nitrogen is added to increase the lifetime of the catalyst by reducing coke formation or
2-1
KKEK 4281 Design Project Chapter 2: Process Description
Group 6 Acrylic Acid Project
any undesired adsorption. [4] The gaseous phase products of this reaction consist of air, water vapour, acrolein, acetol, and some other minor by product. [3]
2.2.2 Separator, V-100
The separator separated the gaseous product stream from Reactor 1 to liquid stream and gas stream by an internal cooler. The cooling fluid used is cooling water. The purpose of the separation is to recycle back the huge quantity of water in the product stream to avoid wastage. The liquid stream which consists of major proportion of water and acetol will recycle back to Reactor 1 while gas stream consist of major proportion of acrolein and air will proceed to Reactor 2 for oxidation reaction.
2.2.3 Reactor 2, CRV-101
In the second reactor, acrolein is oxidized to form acrylic acid via heterogeneous catalytic exothermic reaction. The catalyst used is Mo10 W2 V3.5 Cu2 Sr
0.8. The
temperature of the
o
reactor is maintained at 260 C by using molten salt cooling jacket. The pressure of the reactor is set at 2 bar. The volume percentage of acrolein, oxygen, nitrogen and water vapour fed to Reactor 2 is 10%, 16%, 64% and 10% respectively. Under these conditions, the conversion of acrolein is 98% and yield of acrylic acid is 94.1%.[5] Steam is added as inert gas to control the rate of the reaction. Air is supplied to provide the oxygen required for the oxidation reaction. The nitrogen consists in air will act as an inert to control the reaction. The gaseous product stream consists of air, water vapour, acrylic acid and acetic acid which is a by product of the reaction, air and water vapour.
2.2.4 Quenching Tower, T-100
The product stream from Reactor 2 is fed into quenching tower to separate out the air and form aqueous solution. Water is fed from the top of the tower and the product stream from the bottom of the tower. Water will ‘wash’ the product stream in counter current flow. Air, water vapour and other minor component exited the tower at the top. Acrylic acid and acetic acid will dissolve in water and form aqueous solution.
2-2
KKEK 4281 Design Project Chapter 2: Process Description
Group 6 Acrylic Acid Project
2.2.5 Extractive Distillation Column, T-101
The aqueous acrylic acid and acetic acid solution is entering extractive distillation column. Due to close volatility between acrylic acid and acetic acid, the mixture cannot be separated by conventional distillation column. The solvent used for the extraction of acetic acid is the mixture of cyclohexane and isopropyl acetate. Polymer inhibitor, diphenylamine with benzoquinone and hydroquinone mono-methyl-ether is also fed to the column to prevent acrylic acid polymerization.
[6]
The solvent and polymer inhibitor
feed from the top while the mixture feed from bottom. The solvent extracted out acetic acid from the mixture and exit at the top of the column. The bottom exit stream consists of acrylic acid with purity 99.7% which is the process final product.
2.2.6 Decanter, X-100
Amount of water will exit along with the extracted stream from extractive distillation column and form two phase liquid, water phase and solvent phase. The water can be separated from the two phase liquid by using a decanter and is recycled back to quenching tower as solvent.
2.2.7 Solvent Recovery Distillation Column, T-102
After the water is separated, the extracted stream entered a distillation column to recover the solvent. The solvent with lower boiling point will exit as distillate while acetic acid and other residual with higher boiling point will exit as bottom product. The distillate solvent has the purity of 99.8% and is recycled back to extractive distillation column. The bottom stream is treated as residual and sent to waste water treatment plant.
2.3 Process Description Glycerol feed is preheated by E-100 and E-101 by heat exchanged with the product stream from Reactor 2, CRV-101 and molten salt from cooling jacket of CRV-101. The glycerol is then vaporized by using thermal oil in E-102. Steam feed is mix with the recycle stream and air feed from air compressor. The mixture is preheated by E-103 by heat exchanged with the product stream of Reactor 1, CRV-100. It is further heated by E104 by thermal oil to a temperature controlled by the temperature transmitter of CRV-
2-3
KKEK 4281 Design Project Chapter 2: Process Description
Group 6 Acrylic Acid Project
100 so that CRV-100 temperature always maintain at optimum reaction temperature of 275 oC.
Both gaseous glycerol and steam-air mixture is fed into CRV-100 by feed nozzle. The feeds undergo catalytic endothermic reaction under 1 atm absolute pressure at CRV-100. It produced acrolein, acetol and some other minor by-product. The product stream is compressed to 2.4 bar by a compressor, K-100 and cooled down by E-103 and E-105 by air-water mixture feed and recycled stream from separator, V-100 respectively.
The cooled acrolein stream is fed to V-100 and separated to liquid stream and gas stream. Liquid stream consist of higher proportion of water. A small portion of liquid stream is purged out to waste treatment plant. The remaining liquid stream’s pressure is reduced by a pressure relief valve to 1 atm and heated up by Reactor 1 product stream via E-105. It is then vaporized by E-106 by using molten salt from Reactor 2 cooling jacket. The vaporized stream is mixed with feed steam and recycled back to CRV-100.
The gas stream from V-100 consists of higher proportion of acrolein. It is fed into Reactor 2, CRV-101 along with make up air from air compressor and make up steam. The feeds undergo catalytic exothermic reaction under 2 bar to from gaseous acrylic Acid, acetic acid and some minor by-product. The reactor temperature is maintained at optimum reaction temperature, 260 oC by using molten salt cooling jacket. The hot molten salt is cooled down by heat exchange with glycerol feed and recycled liquid stream via E-101 and E-106. The acrylic acid product stream is cooled down at E-100 by heat exchanged with glycerol feed and fed into quenching tower, T-100.
In quenching tower water is fed from top stage and acrylic acid product stream is fed from bottom. Acrylic acid stream will cool by the water and exit as liquid stream at bottom while air and some volatile components are discharged as gaseous stream from the top of the tower. The gas stream will eventually treated at waste treatment plant before discharged.
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KKEK 4281 Design Project Chapter 2: Process Description
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The liquid stream consists of acrylic acid, acetic acid and water is fed into extractive distillation column T-101. The solvent used is a mixture of cyclohexane and isoprpyl acetate. Polymer inhibitor, diphenylamine with benzoquinone and hydroquinone monomethyl-ether is also added into T-101 to prevent acrylic acid polymerize in the column. The solvent and polymer inhibitor with higher density is fed from top while the liquid stream is fed from bottom. Under solvent extraction acetic acid will be extracted by the solvent and leave at the top of T-101 along with water. Acrylic acid discharged at the bottom of the column as raffinate is pure acrylic acid with 99.7% purity.
The solvent along with the extracted acetic acid and water is a two phases liquid with water phase and solvent phase. The mixture is fed into decanter, X-100 with water is separated and recycled back to quenching tower, T-100.
The solvent and acetic acid is then fed into solvent recovery distillation column, T-102. The bottom product will become residual of the process and sent to waste treatment plant. The solvent with 99.8% is recovered and recycle back to extraction distillation column, T-101.
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KKEK 4281 Design Project Chapter 2
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2.4 Process Flow Diagram
Figure 2.1: Process Flow Diagram
2-6
KKEK 4281 Design Project Chapter 2
2.4.1 Flow Description Stream Unit Phase Pressure
1
2
3
4
5
6
7
8
9
10
L 160
L 140
L 120
G 101.3
G 101.3
G 101.3
G 240
G 220
G 200
L 200
25 135
157.1 135
230 135
300 135
135.00 0.00 0.00 0.00 0.00 0.00
135.00 0.00 0.00 0.00 0.00 0.00
135.00 0.00 0.00 0.00 0.00 0.00
Unit
11
12
13
14
15
atm
L 200
L 140
L 120
G 101.3
G 300
kPa
o C Temperature kmol/hr Mole Flow Component kmol/hr Glycerin Water Oxygen Nitrogen Acetol Acrolein
Stream Phase Pressure
Group 6 Acrylic Acid Project
o C Temperature kmol/hr Mole Flow Component kmol/hr Glycerin Water Oxygen Nitrogen Acetol
303.8 275 407.7 284.3 101.2 66 3932.41 4201.39 4201.39 4201.39 4201.39 2921.16
135.00 137.22 2.33 0.00 2780.90 3049.90 0.00 205.91 205.91 0.00 774.55 774.55 0.00 12.31 13.10 0.00 21.52 155.61
2.33 3049.90 205.91 774.55 13.10 155.61
2.33 3049.90 205.91 774.55 13.10 155.61
2.33 2.33 3049.90 2884.40 205.91 0.02 774.55 0.03 13.10 12.97 155.61 21.44
16
17
18
19
20
G 300
G 140
G 120
G 101.3
G 200
66 66 105 180 146.06 2775.11 2775.11 2775.11
133.6 50.95
25 144.3 295 304.5 66 980.40 3797.41 3797.41 3797.41 1280.23
0.12 2.21 2.21 2.21 144.22 2740.20 2740.20 2740.20 0.00 0.16 0.16 0.16 0.00 0.03 0.03 0.03 0.65 12.31 12.31 12.31
0.00 50.95 0.00 0.00 0.00
0.00 2.22 2.22 2.22 0.00 0.00 2780.90 2780.90 2780.90 165.52 205.89 205.91 205.91 205.91 205.89 774.52 774.55 774.55 774.55 774.52 0.00 12.31 12.31 12.31 0.13
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KKEK 4281 Design Project Chapter 2 Acrolein Stream Phase Pressure
Group 6 Acrylic Acid Project
Unit
1.07 21
20.37 22
20.37 23
20.37 24
0.00 25
0.00 26
21.52 27
21.52 28
21.52 29
134.17 30
kPa
G 300
G 300
G 200
G 200
G 180
L 101.3
L 101.3
G 101.3
L 101.3
L 101.3
133.6 0.00
25 45.52
65.15 260 170 29 1325.75 1260.00 1260.00 245.90
42.17 69.07 72.88 400.00 1367.05 292.96
51.3 15.49
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.00 9.52 36.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
165.52 215.41 810.52 0.13 134.17 0.00 0.00 0.00 0.00 0.00
400.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.18 15.44
o C Temperature kmol/hr Mole Flow Component kmol/hr Water Oxygen Nitrogen Acetol Acrolein Acrylic acid CO2 Acetic acid Cyclohexane I-P-acetate
165.52 144.42 810.52 0.14 2.69 126.25 5.23 5.23 0.00 0.00
165.52 144.42 810.52 0.14 2.69 126.25 5.23 5.23 0.00 0.00
245.90 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
402.94 144.43 810.51 0.00 2.54 0.58 5.23 0.81 0.00 0.00
162.58 0.15 0.01 0.13 0.14 125.67 0.00 4.42 0.00 0.00
2-8
KKEK 4281 Design Project Chapter 2
Stream Phase Pressure
Unit
31
32
33
34
35
36
37
38
39
40
kPa
L 101.3
L 15
L 15
L 15
L 101.3
L 15
L 15
L 15
L 101.3
L 101.3
32 425.51
87.97 124.70
35.68 593.80
53.97 154.50
63.2 154.50
31.87 439.30
45.66 29.28
31.26 410.00
31.34 410.00
240 619.16
0.19 0.32 0.00 0.00 191.25 233.75 0.00
0.15 124.36 0.06 0.13 0.00 0.00 0.00 0.00
162.62 1.32 4.69 0.00 0.14 191.25 233.75 0.00
154.50 0.00 0.00 0.00 0.00 0.00 0.00 0.00
154.50 0.00 0.00 0.00 0.00 0.00 0.00 0.00
8.13 1.32 4.69 0.00 0.14 191.25 233.75 0.00
8.00 1.32 4.38 0.00 0.00 0.17 15.42 0.00
0.14 0.00 0.30 0.00 0.14 191.08 218.33 0.00
0.14 0.00 0.30 0.00 0.14 191.08 218.33 0.00
0.00 0.00 0.00 0.00 0.00 0.00 0.00 619.16
Unit
41
42
43
44
45
46
47
kPa
L 101.3
L 101.3
L 101.3
L 101.3
L 101.3
L 101.3
L 101.3
236.14 619.16
330 558.66
300 558.66
330 65.70
300 65.70
236.14 619.16
200 619.16
619.16 0.00
0.00 558.66
0.00 558.66
0.00 65.70
0.00 65.70
0.00 619.16
0.00 619.16
o C Temperature kmol/hr Mole Flow Component kmol/hr Water Acrylic acid Acetic acid Acetol Acrolein Cyclohexane I-P-acetate Molten Salt
Stream Phase Pressure
Group 6 Acrylic Acid Project
o C Temperature kmol/hr Mole Flow Component kmol/hr Molten Salt Thermal Oil
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KKEK 4281 Design Project Chapter 2
Group 6 Acrylic Acid Project
2.5 References 1. http://www.esru.strath.ac.uk/EandE/Web_sites/02-03/biofuels/what_biodiesel.htm 2. Hanan Atia, Udo Armbruster, Andreas Martin, Dehydration of glycerol in gas phase using heteropolyacid catalysts as active compounds, 29 May 2008 3. Eriko Tsukuda, Satoshi Sato, Ryoji Takahashi, Toshiaki Sodesawa, Production of acrolein from glycerol over silica-supported heteropoly acids, 27 July 2006 4. Jean-Luc Dubois, Millery (FR); Christophe Duquenne, Zickau (DE); Wolfgang Holderich, Frankenthal (DE), Process For Dehydrating Glycerol To Acrolein, Jul. 8, 2008 5. Won-Ho Lee, Kyung-Hwa Kang; Dong-Hyun Ko; Young-Chang Byun, Method Of Producing Acrylic Acid Using A Catalyst For Acrolein Oxidation, May 7, 2002 6. Otsuki et al., Polymerization Inhibition of Acrylic Acid, July 4, 1972
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
CHAPTER 3: PLANT ECONOMIC AND FEASIBILITY STUDY 3.1
Market Analysis
3.1.1 Global Demand The current global demand capacity for acrylic acid is about 7.5 billion pound/ year at year 2007 [1]
and global demand for raw acrylic acid is forecast to rise by 3.7% per annum in the coming 5
years (2007-2011). [2] The growth is especially high at Asia and China which shown amount of 8% annual growth.
[3]
This is partly due to demand competition for acrylic acid supply with
acrylic ester producers. Acrylic esters make the main product derived from acrylic acid and account for 55% of global demand. [2]
About half of the crude acrylic acid is processed to purified (glacial) acrylic acid, which is further processed both on-site (captive use) and by external downstream users. The other half of crude acrylic acid is transformed into various acrylate esters at the production sites. Identical to glacial acrylic acid, these acrylic esters serve as commercial products, which are further processed both on-site and by external downstream users. Glacial acrylic acid is used in the manufacture of superabsorbing polymers (SAP), which account for 32% of the global demand for acrylic acid. Acrylic acid and basic alkyl esters (methyl, ethyl, butyl and 2-ethylhexyl esters) are used for the manufacture of polymer dispersions, adhesives, super absorbent polymers, flocculants, detergents, varnishes, fibres and plastics as well as chemical intermediates. [4]
Besides, there are number of factors drive demand for acrylic acid. Typically, acrylic acid trends align with the economy; as the economy improves, so does demand for acrylic acid. Products made from acrylic acid have continued at their normal, constant growth rates in spite of economic slowdowns. There has not been a lot of additional acrylic acid capacity added in the recent years.
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study 3.1.2
Group 6 Acrylic Acid Project
Local Demand
Malaysia has the demand of acrylic acid in producing polyacrylates and acrylic ester thus the local market of acrylic acid in different local sectors of industry has good prospect. Currently there is only one manufacturer of acrylic acid in Malaysia which is BASF Petronas Sdn Bhd located at Gebeng, Pahang. [5]
3.1.3
Forecasted Future Demand
The demand for Acrylic Acid to produce polyacylates and acrylic ester is increasing steadily. Table 3.1: Forecasted global growth of the usage of acrylic acid up to year 2011 [6]
3.1.4
Area
Growth (%)
United State
5
Europe
1.6
Asia (China)
8
Average Global Growth
3.5
Production of Acrylic Acid
Based on the average global growth of 3.7% and take the basis of year 2007 Acrylic Acid production, the future production of acrylic acid is forecasted. Table 3.2: Forecasted annual production of acrylic acid up to year 2011 [6], [9]
Year
Forecasted Demand (billion pound per year)
2007
7.50
2008
7.78
2009
8.07
2010
8.37
2011
8.68
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study 3.1.5
Group 6 Acrylic Acid Project
Major Manufacturer of Acrylic Acid Table 3.3: Major manufacturer of acrylic acid [6]
Company
Based
Rohm and Haas
USA
BASF
Germany
Dow Chemical
USA
American Acryl
USA
LG Chemical
Korea
3.1.6 Price of Acrylic Acid The market price of Acrylic Acid at different area Table 3.4: Price of acrylic acid at Asia and USA [7]
3.2
Area
Price (per Metric Ton)
Asia
USD 1800 – 1850
USA
USD 1490
Location of Acrylic Acid Plant
Country – Malaysia Through the harnessing of its oil and gas reserves and the forging of smart partnerships with some of the world’s largest petroleum companies, Malaysia has established the ideal infrastructure to support a vibrant petrochemical industry. (i) Criteria of Chosen: [11] •
Strategic location in the heart of South-East Asia.
•
Gateway to ASEAN and AFTA.
•
(AFTA is a free trade zone in Southeast Asia where member countries include Malaysia, Singapore, Thailand, Philippines, Indonesia, Vietnam, Laos, Myanmar, Cambodia and Brunei. The AFTA agreement supports the effort to relax trade barriers amongst member countries in order to achieve direct trade benefits)
•
Rich reserves of natural gas.
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
•
Political and Economic stability.
•
Developed infrastructure.
•
Government’s commitment
•
Quantity of life.
•
World-class facilities.
•
Integrated infrastructure.
•
Availability of capable workforce and skilled technical manpower.
•
The fast development of China had become a net importer of petrochemical products; her entry into World Trade Organization will also open up new business opportunities for petrochemical manufacturers in Malaysia.
(ii) The GDP of Malaysia as shown as following: [12]
Year
Growth Rate %
2003
4.2
2004
5.2
2005
7.1
2006
5.2
2007
5.9
2008
5.7
(iii) Petrochemical industry in Malaysia The petrochemical industry is an important sector in Malaysia with investments totaling RM6.9 billion as at the end of 2007. [13] Malaysia is an exporter of major petrochemicals products such as ethylene oxides, glycols, oxo-alcohols, styrene monomers and so on. Petrochemical zones in Malaysia: [14] •
Kertih, Terengganu
•
Gebeng, Pahang
•
Pasir Gudang port
•
Tanjung Langsat port
3-4
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study •
Group 6 Acrylic Acid Project
Bintulu, Sarawak
(iv) Export of Acrylic Acid Product With the full implementation of AFTA, petrochemical manufacturers in Malaysia will benefit from a single market. Manufacturers based in Malaysia will also benefit from the access to a much larger Asia Pacific market. With China being a net importer of petrochemicals, Malaysia's 'early harvest' Free Trade Agreement with China will open up new business opportunities for petrochemicals manufacturers in Malaysia. [14]
3.2.2
Plant location
Location: Gebeng, Pahang The development of petrochemicals zones where petrochemical plants are clustered together has created a value chain which ensures the progressive development of petrochemicals activities. Gebeng is another petrochemical hub for multinational players like BASF, Amoco, Kaneka, Eastman and Polyplastics.
[11]
The petrochemical zone provides an integrated environment that
meets specific needs of the petrochemical industry. (i) Factors: [11] •
Availability of land.
•
Strategic location for import of raw material and export of products.
•
Logistics gateway for the East Coast Economic Region (ECER) to the Asean and the Asia-Pacific regions
•
Eastern Corridor Incentives
•
Penisular Gas Utilisation (PGU) project which trans-peninsular gas transmission pipeline channels sales gas to industries around the country.
•
Centralised Utility Facilities (CUF) which provides sufficient supply of utilities such as power, industrial gases, water and steam.
•
Kuantan Port 9 Centralised tankage facilities. 9 Pipeline and piperack system connecting Gebeng to Kuantan Port. 9 Container and bulk liquid port.
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
9 Railway linking Kerteh, Gebeng and Kuantan Port. •
East Coast Highway.
•
Environment Technology Part which incorporating a training centre, a waste collection and processing centre as well as raw material management and storage facilities, maintenance and servicing facilities.
(ii) Petrochemical Plant in Gebeng Table 3.5: Petrochemical plant in Gebeng [11]
Petrochemical Plants
Products Acrylic Acid and Esters, Syngas, Butyl Acrylate, Oxo-alcohols, Phthalic Anhydride
BASF Petronas Chemical (M) Sdn Bhd
and Plasticizers, Butanediol, Tetrahydrofurane and Gamma-butyrolactone
Eastman Chemicals (M) Sdn Bhd
Polyester Copolymers
Amoco Chemicals (M) Sdn Bhd
Purified Terephthalic Acid
Kaneka Paste Polymers Sdn Bhd
Dispersion Polyvinyl Chloride
Kaneka Malaysia Sdn Bhd
Methyl Methacrylates Copolymers
Polypropylene (M) Sdn Bhd
Polypropylene
3.3
Government Policy-Taxation [16]
3.3.1
Company Tax
A company, whether resident or not, is assessable on income accrued in or derived from Malaysia. Income derived from sources outside Malaysia and remitted by a resident company is exempted from tax, except in the case of the banking and insurance business, and sea and air transport undertakings. A company is considered a resident in Malaysia if the control and management of its affairs are exercised in Malaysia. Effective from the year assessment of 2007, the company income tax rate be reduced to 27%, including for SMEs.
3-6
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study 3.3.2
Group 6 Acrylic Acid Project
Real Property Gain Tax
Capital gains are generally not subject to tax in Malaysia. Real property gains tax is charged on gains arising from the disposal of real property situated in Malaysia or of interest, options or other rights in or over such land as well as the disposal of shares in real property companies. The tax rates for Malaysian citizens and permanent residents are as follows: Disposal within 2 years 30% Disposal in the 3rd year 20% Disposal in the 4th year 15% Disposal in the 5th year 5% Disposal in the 6th year and thereafter - Company 5% - Individual nil
Citizens and permanent residents also enjoy an exemption of RM5, 000 or 10% of the gains whichever is the greater, besides a one-time tax exemption on the gains arising from the disposal of one private residence. For non-citizens and non-permanent resident individuals, gains from the disposal of real property within five years are taxed at a flat rate of 30%, after which the tax rate will be 5%.
3.3.3
Sales Tax
Sales tax is generally at 10%. However, raw materials and machinery for use in the manufacture of taxable goods are eligible for exemption from the tax, while inputs for selected non-taxable products are also exempted.
3.3.4 Import Tax Malaysia is committed to the ASEAN Common Effective Preferential Tariffs (CEPT) scheme under which all industrial goods traded within ASEAN are imposed import duties of 0% to 5%.
3.4
Economic Evaluation
The main purpose of this study is to calculate the profit which could be generated if the product is selling at the current market value. With the profit, we can determine the period where the generated income can be compensate with the investment made throughout the project.
3-7
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
The cost measurement can be divided into few elements: I. Total Capital Investment II. Total Product Cost III. Profitability Analysis
3.4.1
Purchased Equipment Table 3.6: Estimation of equipment cost [17], [18]
No.
Equipment Type
Quantity
Unit Price
Total
1
Storage Tank 1
5
71521
357605
2
Storage Tank 2
5
77629
388145
3
Storage Tank 3
5
70781
353905
4
Distillation Column
2
408697
817394
5
Quenching Tower
1
123301
123301
6
Reactor 1
1
473200
473200
7
Reactor 2
1
139700
139700
8
E-101 & E-100
2
13346
26692
9
E-104
1
63000
63000
10
E105
1
50600
50600
11
E-103
1
81400
81400
12
Separator
1
27800
27800
13
Compressor
1
1900000
1900000
14
Pump
30
4500
135000
15
Cooling Tower
11
520100
5721100
16
Treatment Cost
1
2500000
1769500
17
Reboiler
3
947000
2841000
Total (USD)
15269342
Total (MYR)
50388828.6
Total Capital Cost (After Index Factor)
57415993.1
3-8
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study 3.4.2
Group 6 Acrylic Acid Project
Total Capital Investment
Total capital investment can be defined as the sum of the fixed-capital investment and the working capital. Total capital investment is evaluated by using fraction of delivered equipment method. Table 3.7: Estimation of Total Capital Investment [19]
Fraction of Delivered
Cost (MYR)
Equipment Direct Cost Cost of Purchased Equipment, E'
60895750.00
Delivery, 10% E'
6089575.00
Subtotal: Delivery Equipment
66985325.00
Purchased Equipment Installation
0.47
31483102.75
Instrumentation & Controls (Installation)
0.36
24114717.00
Piping (Installed)
0.66
44210314.5
Electrical System (Installed)
0.11
7368385.75
Building (Including Services)
0.18
12057358.5
Yard Improvements
0.1
6698532.5
Service Facilities (Installed)
0.7
46889727.5
Land
0.06
4019119.5 176841258
Total Direct Cost, A
Indirect Cost Engineering and Supervision
0.33
22105157.25
Construction Expenses
0.41
27463983.25
Legal Expenses
0.04
2679413
Contractor's Fees
0.22
14736771.5
Contingency
0.44
29473543
Total Indirect Cost, B
96458868
3-9
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project 273300126
Fixed Capital Investment (FCI) = A+B
3.4.3
Working Capital (15% of FCI), C
40995018.90
Total Capital Investment (TCI) = A+B+C
314295144.9
Total Product Cost
Product: Acrylic Acid Targeted Operating Time, day/ year: 330 day/ year Targeted Capacity, tonne/ day: 215.448 tonne/ day Table 3.8: Estimation of Total Product Cost [19]
Suggested Factor
Calculated Value
Manufacturing Cost A. Direct Production Cost Raw Material (Glycerol)
74652732.00
Catalyst
526694.00
Utilities
30585365.00
Opearating Labor
0.10 of TPC
26514140.00
Laboratory Charges
0.10 of OL
2651414.00
Operating Supervision
0.10 of OL
2651414.00
Maintenance and Repairs
0.05 of FCI
13665006.30
Operating Suppliers
0.10 of FCI
27330012.60
Insurance
0.01 of FCI
2733001.26
Local Taxes
0.02 of FCI
5466002.52
Financing
0.03 of TCI
9428854.35
C. Plant Overhead Cost
0.10 of TPC
26514140.00
B. Fixed Charges
General Expenses
3-10
KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
Administrative Costs
0.03 of TPC
7954242.00
Distribution and Marketing Costs
0.08 of TPC
21211312.00
Research and Development Costs
0.05 of TPC
13257070.00
Total Product Cost
265141400.04
Revenue
410590026.00
Gross Profit (Before Tax)
145448625.96
Tax
0.28
Net Profit After Tax
104723010.69
Depreciation
0.05 of FCI
13665006.30 91058004.39
Annual Income (Including Depreciation)
3.4.4
40725615.27
Profitable Analysis
(i) Simple Payback Period Payback period is defined as the minimum length of time for the total return to equal the capital investment. Payback Period =
(ii) Compounded Payback Period Table 3.9: Estimation of payback period [19]
End
Cumulative PW
Present worth
Cumulative PW
at i=0%/year
of cash flow at
at MARR =
through year k
i=10%/year
10%/year
-314295144.9
-314295144.9
-314295144.9
-314295144.9
0.9091
91058004.39
-223237140.5
82780831.79
-231514313.1
2
0.8264
91058004.39
-132179136.1
75250334.83
-156263978.3
3
0.7513
91058004.39
-41121131.73
68411878.7
-87852099.58
4
0.683
91058004.39
49936872.66
62192617
-25659482.58
5
0.6209
91058004.39
140994877.1
56537914.93
30878432.34
Present Worth
Net cash
Factor (P/F)
flow
0
-314295144.9
1
of year
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
6
0.5645
91058004.39
232052881.4
51402243.48
82280675.82
7
0.5132
91058004.39
323110885.8
46730967.85
129011643.7
8
0.4665
91058004.39
414168890.2
42478559.05
171490202.7
9
0.4241
91058004.39
505226894.6
38617699.66
210107902.4
By using the compounded payback period, Payback Period =
(iii) Rate of Return Rate of Return = (Net Profit/ Total Investment) x 100 Rate of Return = 28.97%
(iv) Internal Rate of Return (IRR) Internal Rate of Return = 28.28%
3.5 Conclusion Since the Internal Rate of Return (IRR) is greater than the Minimum Attractive Rate of Return (MARR), the plant is worth to invest. Furthermore the payback period is around 4-5 years according to the calculation. Hence from the economic evaluation, it can be concluded that our project is economical feasible and relatively good future.
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
3.5 References 1. http://www.freedoniagroup.com/Acrylic-Acid-And-Derivatives.html 2. http://mcgroup.co.uk/researches/A/03/Acrylic%20Acid%20Market%20Research.html 3. http://www.icis.com/v2/chemicals/9074869/acrylic-acid/pricing.html 4. http://mcgroup.co.uk/researches/A/03/Acrylic%20Acid%20Market%20Research.html 5. http://www.chemicals-technology.com/projects/gebeng/ 6. http://www.icis.com/v2/chemicals/9074870/acrylic-acid/uses.html 7. http://www.icispricing.com/il_shared/Samples/SubPage219.asp 8. http://www.chemicals-technology.com/projects/gebeng/ 9. http://www.icis.com/v2/chemicals/9074870/acrylic-acid/uses.html 10. http://www.icispricing.com/il_shared/Samples/SubPage219.asp 11. http://www.mida.gov.my/beta/pdf/MIDA%20Petrochemical%202007.pdf 12. http://www.indexmundi.com/malaysia/gdp_real_growth_rate.html 13. http://www.aseansources.com/jsp/malaysia_petrochemical_polymer.jsp 14. http://www.mida.gov.my/en/view.php?cat=5&scat=9&pg=641 15. http://www.ktak.gov.my/template01.asp?contentid=306 16. http://e-directory.com.my/doc/taxation.htm 17. http://www.mhhe.com/engcs/chemical/peters/data/ce.html 18. www.matche.com 19. Peter, M. S., Timmerhaus, K. D.; Plant Design and Economics for Chemical Engineers, 5th Edition, McGraw-Hill Inc: New York, 2003.
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KKEK 4281 Design Project Chapter 3: Plant Economy and Feasibility Study
Group 6 Acrylic Acid Project
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
CHAPTER 4: ENVIRONMENT, SAFETY AND HEALTH 4.1 Environment 4.1.1
Law and Regulation
In Malaysia, the environmental matter is handled by the Department of Environment (DOE), a department constituted under the Ministry of Science, Technology and Environment. The pollution control and strategy or remedial approach is implemented through the enforcement of the Environmental Quality Act, 1974. This act provides for the prevention, abatement, and control of pollution through licensing, and mandates the conducting of an Environmental Assessment Report.
The enforcement of this act and the accompanying 16 sets of Regulations and Orders have played a significant role in the management of the environment, and in particular, with respect to pollution control. Examples of the regulations have to be concern under Environment Quality Act, 1974 are: •
Environment Quality (Clean Air): Regulation 1978
•
Environmental Quality (Sewage and Industrial Effluents): Regulations 1979
•
Environmental Quality (Schedule wastes): Regulation 1989
4.1.2 Waste Water Treatment The waste water stream from production mainly contaminate by following contaminants. Table 4.1: Waste water composition
Mass flow
Mole flow
Concentration
Waste water
(kg/hr)
(kgmole /hr)
(ppm)
Glycerol
10.741
0.11663
3952.228846
Water
2599.2
144.28
-
Acetol
48.042
0.64853
17677.40231
Acrolein
59.724
1.0653
21975.87893
Total
2717.707
146.11046
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
1,2-Ethanedithiol Waste Water
meta-xylylenediamine
Flocculants
Flocculant tank Reactor
Reactor
Clarifier
Filter press
Sludge
halophilic bacteria
NaCl, Mg2+, K+, NH4+, PO43-
Discharge
Carbon Filter
Biological treatment system Membrane Bioreactor
Figure 4.1: Schematic of water treatment system
The flow rate of water is estimated 2717.7liter per hour. The waste water stream is stored in a stabilizer tank. The waste water stream is treated by chemical precipitation method as primary treatment and biological treatment as secondary treatment.
In primary treatment, the waste water stream is dosing with 1,2-Ethanedithiol and metaxylylenediamine in a reactor to remove acrolein and acetol. Dosing 1,2-Ethanedithiol at a pH of between 3.0 and 7.0 to form an acrolein derivative in a process stream to remove acrolein.[1] The polyamine interacts with or binds the carbonyl bearing impurities including acetol. Dosing meta-xylylenediamine can reduce the concentration of acetol. [2]
After the chemical precipitation process, the waste water then is dosing with flocculants for flocculation before flow into the clarifier. The bottom outlet is then pumped through
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
the filter press for dewatering process. Sludge generated is sent for disposal and the effluence water is pump to biological treatment system.
The biological treatment system used is membrane bioreactor. By adding halophilic bacteria into the solution and addition of ions NaCl, Mg2+, K+, NH4+, PO43- to enhance growth can remove the glycerol inside the waste water.
The treated water is filter by carbon filter to remove the remaining organic matter and reduce the COD before discharge out. The discharge waste water have following target. Table 4.2: Waste water discharge target
Concentration
After chemical
After biological
Waste stream
(ppm)
precipitation (ppm)
treatment
Glycerol
3952.228846
3952.228846
0
Acetol
17677.40231
0
0
Acrolein
21975.87893
0
0
The sludge / precipitate are then destroyed by controlled burning in an incinerator. 4.1.3 Gas Emmision and Treatment
Purge
Discharge
Scrubber System
Carbon Filter Figure 4.2: Schematic of gas treatment system
The gas emission from the plant mainly containing acrylic acid, acetic acid, acrolein and carbon dioxide.
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
Acrylic acid and acetic acid in gas phase can be neutralized by wet scrubber with caustic solution as scrubbing fluid.
[3]
Emissions of acrolein and other odorous components in
vents can be controlled with water scrubbers. [4]
Hence the purge gas is flow through scrubber system to remove the acrylic acid, acetic acid and acrolein. The concentration of carbon dioxide discharge is 0.6% which is insignificant which do not need addition treatment. Before the gas discharge to environment, the gas is flow through the carbon filter to filter out the remaining organic compounds. Removal of air pollutants by adsorption onto granules of activated carbon is an extremely effective technology for volatile organic compounds (VOCs) and other organic pollutants. [3]
The target of the gas treatment plant can simply in following table: Table 4.3: Gas emission target
Concentration
After Scubber
After Carbon
Waste stream
(ppm)
(ppm)
Filter(ppm)
Acrylic Acid
1022.686871
10
5
Acetic Acid
1282.029479
10
5
Acrolein
4059.200779
0.1
0.05
The water used for absorb the acrolein is sent to waste water treatment plant before discharge out. The granular activated carbon can be regenerated by controlled burning in the incinerator too. [5]
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
4.2 Health 4.2.1 Effect to Human 4.2.1.1 Acetic Acid 4.2.1.1.1 Health Hazard Glacial acetic acid is a highly corrosive liquid. Contact with the eyes can produce mild to moderate irritation in humans. Contact with the skin may produce burns. Ingestion of this acid may cause corrosion of the mouth and gastrointestinal tract. Death may occur from a high dose (20–30 mL), and toxic effects in humans may be felt from ingestion of 0.1–0.2 mL. An oral LD50 value in rats is 3530 mg/kg. Glacial acetic acid is toxic to humans and animals by inhalation and skin contact. In humans, exposure to 1000 ppm for a few minutes may cause eye and respiratory tract irritation. Rabbits died from 4-hour exposure to a concentration of 16,000 ppm in air.
4.2.1.1.2 Exposure Limits TLV-TWA 10 ppm (25 mg/m3) (ACGIH, OSHA, and MSHA); TLV-STEL 15 ppm (37.5 mg/m3) (ACGIH).
4.2.1.2 Acetol 4.2.1.2.1 Health Hazard Acetol is flammable liquid and vapor. It may cause eye and skin irritation. Ingestion of acetol may cause irritation of the digestive tract. Inhalation may cause respiratory tract irritation. Vapors may cause dizziness or suffocation. An oral LD50 value in rats is 2200 mg/kg.
4.2.1.2.2 Exposure Limits Not listed in ACGIH, OSHA and NIOSH.
4.2.1.3 Acrolein 4.2.1.3.1 Health Hazard Acrolein is one of the EPA Classified Acute Hazardous Waste. It is a highly toxic compound that can severely damage the eyes and respiratory system and burn the skin.
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
Ingestion can cause acute gastrointestinal pain with pulmonary congestion. An oral LD50 value in mice is 40 mg/kg.
Inhalation can result in severe irritation of the eyes and nose. A concentration of 0.5 ppm for 12 minutes can cause intolerable eye irritation in humans. In rats, exposure to a concentration of 16 ppm acrolein in air for 4 hours was lethal. Acrolein can be absorbed through the skin. The spillage of liquid can cause severe chemical burns. Skin contact may lead to chronic respiratory disease and produce delayed pulmonary edema. In a study on inhalation toxicity in rats, the exposure to 1 atm of acrolein vapors caused physical incapacitation. The animals lost the ability to walk and expired.
4.2.1.3.2 Exposure Limits TLV-TWA 0.25 mg/m3 (0.1 ppm) (ACGIH and OSHA); STEL 0.8 mg/m3 (0.3 ppm); IDLH 5 ppm (NIOSH).
4.2.1.4 Acrylic Acid 4.2.1.4.1 Health Hazard Acrylic acid is a corrosive liquid that can cause skin burns. Spill into the eyes can damage vision. The vapors are an irritant to the eyes. The inhalation hazard is of low order. An exposure to 4000 ppm for 4 hours was lethal to rats. The dermal LD50 value in rabbits is 280 mg/kg.
4.2.1.4.2 Exposure Limits TLV-TWA 10 ppm (30 mg/m3) (ACGIH).
4.2.1.5 Carbon Dioxide 4.2.1.5.1 Health Hazard Carbon dioxide is an asphyxiant. Exposure to about 9–10% concentration can cause unconsciousness in 5 minutes. Inhalation of 3% CO2 can produce weak narcotic effects. Exposure to 2% concentration for several hours can produce headache, increased blood pressure, and deep respiration.
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
4.2.1.5.2 Exposure Limits TLV-TWA 5000 ppm (9000 mg/m3) (ACGIH, MSHA, and OSHA); STEL 30,000 ppm (ACGIH).
4.1.1.6 Glycerol 4.2.1.6.1 Health Hazard Glycerol is a clear, colorless solution with a faint to slight odor. It may cause eye and skin irritation. Ingestion of large amounts may cause gastrointestinal irritation. It is low hazard for usual industrial handling. Inhalation of a mist of this material may cause respiratory tract irritation.
4.2.1.6.2 Exposure Limits TLV-TWA: 10 mg/m3 (ACGIH), 15mg/m3 (OSHA), TLV-STEL: 20mg/m3
4.2.2 Effect to Environment 4.2.2.1 Acetic Acid Environmental effects depend on the concentration and duration of exposure to acetic acid. In high concentrations it can be harmful to plants, animals and aquatic life. Acetic acid degrades rapidly to harmless substances in the environment.
4.2.2.2 Acrolein In view of the high toxicity of acrolein for aquatic organisms, it presents a risk to aquatic life at, or near, sites of industrial discharges or spills, and during biocidal use. Contamination of soil, water, and the atmosphere can be avoided by the use of proper methods of storage, transport, and waste disposal.
4.2.2.3 Acrylic Acid Acrylic acid emitted into the atmosphere will react with photochemically produced hydroxyl radicals and ozone, resulting in rapid degradation. There is no potential for long-range atmospheric transport of acrylic acid because it has an atmospheric lifetime of less than one month. When released into water, acrylic acid readily biodegrades. The fate
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KKEK 4281 Design Project Chapter 4: Safety, Health and Environment
Group 6 Acrylic Acid Project
of acrylic acid in water depends on chemical and microbial degradation. When added to water acrylic acid is rapidly oxidized, and so it can potentially deplete oxygen if discharged in large quantities into a body of water. Acrylic acid has been shown to be degraded under both aerobic and anaerobic conditions. The toxicity of acrylic acid to bacteria and soil microorganisms is low.
4.2.2.4 Glycerol Acute toxicity of glycerol to fish, daphnia, algae and microorganisms has been test. The studies show that glycerol is of low acute toxicity to fish and aquatic invertebrates. LC/EC50 values are all in excess of 5000 mg/L.
4.3 Safety 4.3.1 Hazard Introduction The term hazardous properties may be broadly classified into two principal categories: namely toxicity, and flammability and explosivity.
The term toxicity refers to substances that produce poisoning or adverse health effects upon acute or chronic exposure. It includes mutagenicity and carcinogenic potential, teratogenicity and corrosivity or irritant actions.
Animal data on the median lethal dose (LD50) by various routes of administration is good indicator of the degree of toxicity of a substance. Substances that exhibit acute oral LD50 values of 500 mg/kg are termed moderate and low toxicants, respectively.
The flammable properties of substances in air include their flash point, vapor pressure, autoignition temperatures, and flammability range. Liquids that have a flash point of 10000 and 0.7
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