Proyecto mtbe indonesia


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Proyecto mtbe indonesia

  2. 2. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR ACKNOWLEDGEMENT First and foremost, thank you to Allah S.W.T for giving us the strength to finish up this project report. Without Your Willingness we would not be able to complete this project. It would be impossible to acknowledge adequately all the people who have been influential, directly or indirectly in forming this project. We would like to take this opportunity to express our deepest gratitude to our supervisors, Encik Mohd Imran Bin Zainuddin and Puan Sunita Binti Jobli who has given us his constant encouragement constructive advises and his patient in monitoring our progress in this project. Our appreciation and special thanks goes, Puan Hasnora Binti Jafri, Puan Junaidah Binti Jai, Encik Aziz Bin Ishak for supplying the valuable information and guidance for this project. We greatly indebted to Encik Napis Bin Sudin for his cooperation and willingness to be interviewed and for provide us with invaluable information and for his resourcefulness in gathering material. Special thanks owe to Puan Masni Bt Ahmad for her willingness to be interviewed and for the painstaking care she has shown in assisting us throughout the project. We also would like to express our appreciation to the Malaysia Industrial Development Authority (MIDA), Pusat Informasi Sirim Berhad, Petronas Resource Center, Jabatan Perangkaan Malaysia and Tiram Kimia Sdn.Bhd. (Kuala Lumpur) for their generous supply of relevant documents and material needed research. Last but not least to all my lecturers, family, friends and collegues for their encouragement and kind support when we need it most. 2
  3. 3. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR ABSTRACT The purpose for this MTBE or Methyl tertiary Butyl Ether plant is to produce 300,000 metric tonne/year. MTBE is the simplest and most cost effective oxygenate to produce, transport and deliver to customers. The additive works by changing the oxygenate / fuel ratio so that gasoline burns cleaner, reducing exhaust emissions of carbon monoxide, hydrocarbons, oxides of nitrogen, fine particulates and toxic. Two units will be considered which are the fluidizations, (Snamprogetti) Unit and the Etherification Unit. The raw materials used are isobutane, methanol, and water as feedstock. In addition, two types of catalysts are chromia alumina catalyzed compound in Snamprogetti Unit, while sulphonic ion exchanged resin catalyzed is used in the MTBE reactor. A good deal of catalyst has been devoted to improve the activity, selectivity, and the lifetime of the catalysts. In the Design Project 2, we emphasize in the individual chemical and mechanical designs for selected equipments in the plant. The chosen equipments are Catalytic Cracking Reactor, Multitubular Fixed Bed Reactor, MTBE Distillation Column, LiquidLiquid Extraction Column and Heat Exchanger. Design Project 2 also includes Process Control, Safety, Economic Evaluation, Process Integration and as well as Waste Treatment, which are considered as group works. 3
  4. 4. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CONTENTS TITLE PAGE DECLARATION II CERTIFICATION III ACKNOWLEDGEMENT V ABSTRACT VI LIST OF TABLES LIST OF FIGURES LIST OF NOMENCLATURES REPORT 1 CHAPTER 1 PROCESS BACKGROUND AND INTRODUCTION 1.1 Introduction 1.2 Historical Review of MTBE Production Process 1.2.1 UOP Oleflex Process 1.2.2 Philips Star Process 1.2.3 ABB Lummus Catofin Process 1.2.4 Snmprogetti Yartsingtez FBD Process 1 2 3 3 3 4 CHAPTER 2 PROCESS SELECTION 2.1 2.2 Method Consioderation Detailed Process Description 2.2.1 Snaprogetti Yarsingtez fbd Process 2.2.2 MTBE Unit 2.2.3 Distillation Column Unit 2.2.4 Liquid-Liquid Extraction Unit 5 7 7 8 8 9 CHAPTER 3 ECONOMIC SURVEY 3.1 3.2 3.3 3.4 Market Survey 3.1.1 World Market Asia Market Demand Production Capacity 10 10 11 11 14 4
  5. 5. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.5 3.6 3.7 Supply Market Price 3.6.1 Methanol 3.6.2 Isobutane 3.6.3 Catalyst 3.6.4 Conclusion Economic Analysis 3.7.1 Break Even Analysis 3.7.2 Data Calculation1 14 15 15 16 16 16 17 17 20 CHAPTER 4 PLANT LOCATIONS & SITE SELECTION 4.1 4.2 4.3 4.4 Plant Location 24 General Consideration On the site Selection 24 4.2.1 Location with Respect To Marketing Area 25 4.2.2 Raw Material supply 25 4.2.3 Transport Facilities 25 4.2.4 Availability Of Labor 25 4.2.5 Availability Of Utilities 26 4.2.6 Environmental Impact and Effluent Disposal 26 4.2.7 Local Community Considerations 26 4.2.8 Land (Site Consideration) 26 4.2.9 Political and Strategic Consideration 27 Overview on Prospective Locations 27 4.3.1 Teluk Kalong 28 4.3.2 Tanjung Langsat 28 4.3.3 Bintulu 29 Conclusion 33 CHAPTER 5 ENVIRONMENTAL CONSIDERATION 5.1 5.2 5.3 Introduction Stack gas 5.2.1 Gas Emission treatment Wastewater Treatment 5.3.1 Wastewater characteristic 5.3.1a) Priority pollutants 5.3.1b) Organic 5.3.1c) Inorganic 5.3.1d) pH and Alkalinity 5.3.1e) Temperature 5.3.2 Liquid waste treatment 5.3.2a) Equalization treatment 5.3.2b) Solid waste treatment 5.3.3 Waste Minimization 34 35 35 35 35 36 36 37 37 38 38 38 39 41 5
  6. 6. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CHAPTER 6 SAFETY CONSIDERATION 6.1 6.2 6.3 Introduction 42 Material Safety Data Sheet 43 6.2.1 Isobutane 43 Product Information 43 Physical & Chemical Properties 43 Immediate Health Effects 44 First Aid Measure 44 6.2.2 N-Butane 44 Handling and Storage 45 6.2.3 Methanol 45 6.2.4 MTBE 46 Physical State and Appearance46 Physical Dangers 46 Chemical Dangers 47 Inhalation Risks 47 6.2.5 TBA 47 Recognition 48 Evaluation 48 Controls 48 Hazard Identification & Emergency Safety & Health Risk 49 CHAPTER 7 MASS BALANCE 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 Snamprogetti -Yarsingtez FBD Unit Separator Mixer MTBE Reactor 7.4.1 1st Reaction in rector 7.4.2 2nd Reaction in reactor 7.4.3 3rd Reaction in reactor 7.4.4 Overall reaction Distillation Column Liquid Extraction Column Distillation Column Overall reaction system; flow diagram Scales Up Factor 51 53 53 54 55 56 57 58 59 60 61 62 63 CHAPTER 8 ENERGY BALANCES 8.1 8.2 Energy Equation Energy balance: Sample of calculation 8.2.1 Pump 1 8.2.2 Cooler 1 8.2.3 Separator 8.2.4 MTBE Reactor 8.2.5 Pump 2 64 65 73 75 76 78 79 6
  7. 7. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 8.2.6 8.2.7 8.2.8 8.2.9 8.2.10 8.2.11 8.2.12 8.2.13 8.2.14 8.2.15 8.2.16 Mixer Expander 1 Cooler 1 Distillation Column 1 Cooler 2 Pump 3 Extraction Column Pump 4 Pump 5 Distillation Column 2 Cooler 3 CHAPTER 9 HYSYS 80 81 82 84 86 87 88 89 91 92 93 95 APPENDICES REPORT 2 CONTENTS PAGE CHAPTER 1 CHEMICAL DESIGN AND MECHANICAL DESIGN SECTION 1 CATALYTIC CRACKING DESIGN 2.2 1.1 Introduction 1.2 Estimation of Cost Diameter of Reactor 1.3 Calculation of TDH Height 1.4 Minimum Fluidization Velocity 1.5 Calculation for Terminal Velocity 1.6 Find the Value Kih 1.7 Find the value Eo 1.8 Calculation of Solid Loading 1.9 Calculation for Holding Time 1.10 Calculation for Pressure Drop 1.11 Determine the Direction and Flowrate 1.12 Design of Cyclone 1.13 Calculation for Mechanical Design Mechanical Design 2.2.1 Introduction 2.2.2 Design stress 2.2.3 Welded Joint Efficiency 1 3 4 4 5 8 9 10 12 14 15 17 21 58 59 59 7
  8. 8. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 2.2.4 2.2.5 2.2.6 2.2.7 2.2.8 2.2.9 2.2.10 2.2.11 2.2.12 2.2.13 2.2.14 2.2.15 2.2.16 2.2.17 2.2.18 2.2.19 2.2.20 2.2.21 Corrosion allowance Minimum thickness of cylindrical section of shell Minimum thickness of domed head Loading stress Dead weight load Dead Weight of Vessel Weight of the Tubes Weight of Insulation Weight of Catalyst Total Weight Wind Loading Analysis of Stresses Dead Weight Stress Bending Stress Radial Stress Check Elastic Stability Vessel Support Skirt Thickness Height of the Skirt Bending Stress at Base of the Skirt Bending Stress in the Skirt Base Ring and Anchor Bolt Design Compensation for Opening and Branches Compensation for Other Nozzles Bolted Flange Joint Type of Flanges Selected Gasket Flange face SECTION 3 3.1 3.2 3.3 3.4 59 59 60 61 61 61 62 62 63 63 63 64 65 65 66 67 68 68 69 70 70 71 73 74 74 74 75 75 MTBE DISTILLATION COLUMN Introduction Selection f Construction Material Chemical Design 3.3.1 Determine the Number of Plate 3.3.2 Determination of Number of Plate 3.3.3 Physical Properties 3.3.4 Determination of Column Diameter 3.3.5 Liquid Flow Arrangements 3.3.7 Plate Layout 3.3.8 Entrainment Evaluation 3.3.9 Weeping Rate Evaluation 3.3.13 Number of Holes 3.3.14 Column size Mechanical Design 3.4.1 Material construction 3.4.2 Vessel Thickness 3.4.3 Heads and closure 3.4.4 Total Column Weight 78 79 79 81 88 89 89 90 91 91 94 95 96 98 98 99 8
  9. 9. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.5 3.4.5 Wind Loads 3.4.6 Stiffness Ring Vessel Support Design SECTION 4 4.1 4.2 4.3 5.1 5.2 5.3 DESIGN OF LIQUID-LIQUID EXTRACTION COLUMN Introduction Chemical Design 4.2.1 Choice of Solvent 4.2.2 Estimation the Physical Properties 4.2.3 Determination the Number of Stage 4.2.4 Sizing of Sieve Tray 4.2.5 Number of Holes 4.2.6 Column Parameter 4.2.7 Weeping Evaluation Mechanical Design 4.3.1 Material Construction 4.3.2 Vessel Thickness 4.3.3 Design of Domed Ends 4.3.4 Column Weight Dead Weight of Vessel Weight of Plate Weight of Insulation Total weight Wind Loading 4.3.5 Analysis of Stress 4.3.5. 1 Longitudinal & Circumferential Pressure Stress Dead weight Bending Stress Buckling 4.3.6 Vessel Support Design Skirt Support Base Ring and Anchor 4.3.7 Piping Sizing SECTION 5 100 100 100 103 104 104 104 105 107 107 107 108 110 111 111 112 112 113 113 113 114 114 115 115 115 115 116 117 117 119 122 HEAT EXCHANGER DESIGN Introduction 5.1.1 Designing the heater Chemical Design 5.2.1 Physical Properties of the Stream 5.2.2 The Calculation 5.2.3 Number of Tubes Calculation 5.2.4 Bundle and Shell Diameter 5.2.5 Tube Side Coefficient 5.2.6 Shell Side Coefficient 5.2.7 Overall Heat Transfer Coefficient 5.2.8 Tube Side Pressure Drop 5.2.9 Shell Side pressure Drop Mechanical Design 5.3.1 Design Pressure 127 129 130 130 131 133 134 135 137 139 140 140 142 142 9
  10. 10. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.3.7 5.3.8 5.39 5.3.10 5.3.11 5.3.12 5.3.13 5.3.14 5.3.15 Design Temperature Material of Construction Exchanger Type Minimum Thickness Longitudinal Stress Circumferential Stress Minimum Thickness of Tube wall Minimum Thickness of Head and Closure Minimum Thickness of the Channel Cover Design Load Pipe Size Selection for the Nozzle Standard Flanges Design Of Saddles Baffles 142 142 143 143 144 144 144 145 146 147 150 150 152 152 CHAPTER 2 PROCESS CONTROL AND INSTRUMENTATION 2.1 2.2 2.3 Introduction Objective of control Control system design sheet 2.3.1 Heat Exchanger 2.3.2 Catalytic cracking fluidized bed reactor 2.3.3 Compressor 2.3.4 Condenser 2.3.5 Separator 2.3.6 Fixed bed reactor 2.3.7 Distillation Column 2.3.8 Liquid -liquid extraction Column 2.3.9 Distillation Column 2.3.10 Mixer 2.3.11 Expander 154 155 156 156 157 158 159 160 161 162 163 164 165 166 CHAPTER 3 SAFETY CONSIDERATION 3.1 3.2 3.3 3.4 Introduction Hazard and Operability Study Plant Start Up and Shut Down Procedure 3.3.1 Normal Start Up and Shut Down the Plant Operating Limits Transient Operating and Process Dynamic Added Materials Hot Standby Emergency Shut Down 3.3.2 Start up and Shut down Procedure for the main Equipment Reactor Distillation Column Liquid-Liquid Extraction Column Heat Exchanger Emergency Response Plan (ERP) 167 168 170 171 171 172 172 172 172 172 172 173 174 175 175 10
  11. 11. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.5 3.4.1 Emergency Response Procedures 3.4.2 Evacuation Procedures 3.4.3 Fires 3.4.4 Explosion, Line Rupture or Serious Leak 3.4.5 Other Emergencies Plant Layout 176 176 177 177 177 178 CHAPTER 4 ECONOMIC EVALUATION 4.1 4.2 4.3 4.4 Introduction Cost Estimation Profitability Analysis 4.3.1 Discounted Cash flow 4.3.2 Net Present Value 4.3.3 Cumulative Cash flow Diagram 4.3.4 Rate of Return 4.3.5 Sensitivity Analysis 4.3.6 Payback Period Conclusion 184 187 199 199 202 203 204 205 206 208 CHAPTER 5 PROCESS INTEGRATION AND PINCH TECHNOLOGY 5.1 5.2 5.3 5.4 5.5 Introduction Pinch Technology The Problem Table Method The Heat Exchanger Network Minimum number of exchangers 209 209 210 214 216 CHAPTER 6 WASTE TREATMENT 6.1 6.2 6.3 6.4 6.5 6.6 Introduction Wastewater Treatment Wastewater Treatment Plant Design Sludge Treatment Waste Treatment Plant Layout Absorption tank using granular activated carbon 6.6.1 Analysis of the absorption process 6.6.2 Breakthrough Absorption capacity 220 221 224 229 230 231 232 233 APPENDICES 11
  12. 12. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR LIST OF TABLES OF DESIGN I TABLE TITLE 1.1 The Physical and Chemical Properties of MTBE 2.1 PAGE 2 The Comparison of the UOP Oleflex, Philips Star SP-Isoether FBD Process 6 3.1 Trade Balance of MTBE in Asia and Pacific 12 3.2 MTBE Balances for Asia and Pacific 13 3.3 Production, Import, Export & Consumption in Europe in Year 2000 14 3.4 Supplies MTBE Plant in Asia & Pacific 15 3.5 Standard Price for Isobutane 16 3.6 Cost of Producing MTBE 500000 tonne/year 18 3.7 Value in US Dollar Converted to RM 20 3.8 Value in US Dollar Converted to RM per tonne 20 3.9 Data Calculation by using Microsoft Excel in RM 23 4.1 The Comparison of the Potential Site Location 30 4.2 The Comparison of Location in term of Weightage Study 31 4.3 The Electricity Tariffs (Industrial Tariff) for Peninsular Malaysia and Sarawak 33 12
  13. 13. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR LIST OF TABLES OF DESIGN II TABLE TITLE PAGE Chapter 1 Section 1 1.1 Calculation for Terminal Velocity in Different Size of dp. 8 1.2 Correlation of Three Investigators 10 1.3 Data Calculation to Find Solid Loading 12 1.4 Summary of Mechanical Design 40 3.1 The Composition in Feed Stream 80 3.2 The Composition in Top Stream 80 3.3 The Composition in Bottom Stream 80 3.4 The Average Relative Volatility, 3.5 The Non-key Flow of the Top Stream 82 3.6 The Non-key Flow of the Bottom Stream 83 3.7 MTBE Equilibrium Curve 85 3.8 Provisional Plate Design Specification 97 3.9 Summarized Results of Mechanical Design 101 3.10 Design Specification of the Support Skirt 102 4.1 Provisional Plate Design Specification 106 4.2 Summary of the Mechanical Design 118 4.3 Stress Analysis for Liquid-Liquid Extraction Column 119 4.4 Design Specification of the Support Skirt 119 4.5 Piping Sizing for Liquid-liquid Extraction Column 120 Section 3 α 82 Section 4 Section 5 5.1 Properties of Raw Material (Isobutane and N-butane) and Steam for (E100) 5.2 130 Summary of Chemical Design For Heat Exchanger In Series 5.3 141 By taking D = 100 mm, the selected tube nozzle 149 13
  14. 14. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR TABLE TITLE PAGE 5.4 By taking D = 500 mm, the selected tube nozzle is: 149 5.5 Standard Flange for Inlet isobutene 150 5.6 Standard Flange for Outlet isobutene 151 5.7 Standard Flange for Inlet Steam 151 5.8 Standard Flange for Outlet Steam 151 5.9 Using Ds = 600mm, the Standard Steel Saddles for Vessels up to 1.2m 5.10 152 Summary of Mechanical Design For Heat Exchanger in Series 153 2.1 Parameter at Heat Exchanger 151 2.2 Parameter at Catalytic Cracking Fluidized Bed Reactor 152 2.3 Parameter at Compressor 153 2.4 Parameter at Condenser 154 2.5 Parameter at Separator 154 2.6 Parameter at Fixed Bed Reactor 155 2.7 Parameter at MTBE Distillation Column 156 2.8 Parameter at Liquid-liquid Extraction Column 157 2.9 Parameter at Distillation Column 158 2.10 Parameter at Mixer 159 2.11 Parameter for Expander 160 Important Features in a HAZOP Study 170 4.1 Labor Cost 189 4.2 Estimation Cost of Purchase Equipment 197-198 4.3 Annual Cash flow Before Tax 200 4.4 Annual Cash flow After Tax 201 4.5 Present Worth Value 202 Chapter 2 Chapter 3 3.1 Chapter 4 14
  15. 15. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 4.6 After Tax Cumulative Cash Flow TABLE 203 TITLE PAGE 4.7 Present Value (RM) When i = 30% & i = 40% 204 4.8 Future Value (RM) When MARR = 15% 205 4.9 Simple Payback Period 206 4.10 The Interpolation Simple Payback Period 206 4.11 Discounted Payback Period 207 4.12 The Interpolation Discounted Payback Period 207 5.1 Shows the process data for each stream. 210 5.2 Interval Temperature for ΔTmin = 10oC 211 5.3 Ranked order of interval temperature 212 5.4 Problem Table 213 Chapter 5 Chapter 6 6.1 Parameter Limits for Wastewater and Effluent under the Environmental Quality Act 1974 6.2 208 Functions of Pumps in the Waste Treatment Plant 215 15
  16. 16. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR LIST OF FIGURES OF DESIGN I FIGURE 3.1 TITLE PAGE MTBE’s Role in US Gasoline grew rapidly Through 1995 10 3.2 World MTBE Demand (1998-2010) – Mod Scenario 11 3.3 MTBE supply & Demand Asia and Pacific 13 3.4 Breakeven Analysis Chart Calculated by using Excel 19 5.1 . Functional Elements in a Solid-Waste Treatment System 40 16
  17. 17. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR LIST OF FIGURES OF DESIGN II FIGURE TITLE PAGE Chapter 1 Section 1 1.1 Illustration Diagram of the Reactor 2 1.2 CDRe2 and CD/Re vs. Reynolds Number 6 Analysis of Stresses 67 3.1 MTBE Distillation Column 78 3.2 McCabe-Thiele Diagram 86 5.1 Heat Exchanger in Series for the Heating Process 129 5.2 Steel Pipe Nozzle 149 5.3 Standard Flange 150 2.1 Control Scheme for the Heat Exchanger 156 2.2 Control Scheme for Catalytic Cracking Section 2 2.1 Section 3 Section 5 Chapter 2 Fluidized Bed Reactor 157 2.3 Control Scheme for the Compressor 158 2.4 Control Scheme for the Condenser 159 2.5 Control Scheme for the Separator 160 2.6 Control Scheme for the Fixed Bed Reactor 161 2.7 Control Scheme for the MTBE Distillation Column 162 2.8 Control Scheme for the Liquid-liquid Extraction Column 163 2.9 Control Scheme for the Distillation Column 164 2.10 Control Scheme for the Mixer 165 2.11 Control Scheme for the Expander 166 17
  18. 18. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR FIGURE TITLE PAGE Chapter 3 3.1 Methyl tert-Butyl Ether (MTBE) Plant Layout 180 3.2 Methyl tert-Butyl Ether (MTBE) Plant Evacuation Routes 181 3.3 PID before HAZOP 182 3.4 PID after HAZOP 183 Cumulative Cash Flow (RM) Versus Year 203 5.1 Diagrammatically representation of process stream 210 5.2 Intervals and streams 211 5.3 Heat Cascade 212 5.4 Grid for 4 stream problem 213 5.5 Grid for 4 Stream Problem 214 5.6 Proposed Heat Exchanger Network 216 6.1 The Sludge Treatment System 229 6.2 Waste Treatment Plant Layout 231 Chapter 4 4.1 Chapter 5 Chapter6 18
  19. 19. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Ar - Archimedes number a - acceleration B - settling chamber longitudinal cross-sectional area b - dimension C - constant CD - drag coefficient c - concentration D - system diameter d - particle diameter de - effective fiber diameter E, - field intensity F - cross-sectional area Pr - Fronde number g - gravitational acceleration H - height K - precipitation constant , A - Cross sectional area of catalytic reactor Aor - Area of orifice C Ag - Concentration of gas reactant CD - Drag coefficient d Bv - Diameter of bubble in the bed dp - Particle diameter D - Diffusivity Dt - Diameter of catalytic reactor e - Thickness E - Activation energy 19
  20. 20. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR FBo - Mass flow of coal to the catalytic reactor FC - Fixed carbon mass fraction Hbed - Height of bed Hh - Height of Catalytic reactor J - Joint factor k” - Reaction rate constant k - Reaction rate constant K eq - Equilibrium constant L - Height above the bed n - Total no of orifice N - No of holes in 1 m2 area Nor - No of orifice in 1 m2 area PCO , PH 2 O - Pi Design stress - Partial pressure rC , rS - Rate of reaction R - Ideal gas constant Ret - Reynolds number Rp - Radius of particle t - Total holding time T - Temperature Uo - Superficial gas velocity Umf - Minimum fluidization velocity Ut - Terminal velocity VBed - Volume of bed WBed - Weight of coal in bed WC - Total mass of carbon X - Conversion factor α - Fitting parameter (for this design is 0.21) β - Fitting parameter (for this design is 0.66) ρg - Gas density ρB - Molar density ρs - Bulk density of catalyst ρp - Particle density 20
  21. 21. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR µg - Gas viscosity τ - Time for complete conversion of reactant particle ∆ p - Pressure drop E - total elutriation rate of particles Ef - frictional force of particles Ei - entrainment rate of panicle size i Ei∞ - elutriation rate of particle size i Eo - total entrainment rate at bed surface E∞ - total elutriation rate of particles g - gravitational acceleration constant gc - gravitational conversion constant, m kg/s2 kg -force Gi - solids flow rate h - height above dense bed surface Rep - particle Reynolds Number = ρ g (U o − U ts ) d p / µ Ret - dpU ρ / µ g t - time Umf - minimum fluidization velocity Uo - superficial gas velocity Usi - solid velocity (upward) Us - single particle terminal velocity of particle size i W - weight fraction of bed Ws - weight of solid particles in verlical pipe having length h Xi - weight fraction of particle size i in bed Greek Symbols ε - voidage in freeboard 21
  22. 22. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR εi - voidage in freeboard for system having only particle size i λ - solid friciion coefficient ρg - gas density ρp - particle density 22
  23. 23. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CHAPTER 1 PROCESS BACKGROUND AND INTRODUCTION 1.1 INTRODUCTION Methyl tertiary butyl ether (MTBE) is produced by reacting isobutene with methanol over a catalyst bed in the liquid phase under mild temperature and pressure. Isobutene can be obtained from stream cracker raffinate or by the dehydrogenation of isobutane from refineries. Ether in general is a compound containing an oxygen atom bonded to two carbon atoms. In MTBE one carbon atom is that of a methyl group – CH3 and the other is the central atom of a tertiary butyl group, -C (CH3)). At room temperature, MTBE is a volatile, flammable, colorless liquid with a distinctive odour. It is miscible with water but at high concentrations it will form an air-vapour explosive mixture above the water, which can ignite by sparks or contact with hot surfaces. MTBE has good blending properties and about 95% of its output is used in gasoline as an octane booster and an oxygenate (providing oxygen for cleaner combustion and reduced carbon monoxide emissions). It is also used to produce pure isobutene from C4 streams by reversing its formation reaction. It is a good solvent and extractant. Table 1.1: The Physical and chemical properties of MTBE 23
  24. 24. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Chemical formula Molecular structure Oxygen content Physical state (at normal C5H12O (CH3)4CO 18.2 wt% Colorless liquid temperature and pressure) Boiling point Melting point Flash point Autoignition temperature Flammable limits in air Relative density Vapour pressure Reactive index Color Water solubility 55.2oC -108.6 oC 30 oC 425 oC 1.5 – 8.5% 0.7405g/ml at 20 oC 245 mm Hg at 25 oC 1.3690 at oC Colorless 42000mg/l at 25 oC (<10% in water, miscible with ethanol and Partition coefficient noctanol/water (log10) Henry’s Law Constant 1.2 diethyl ether) 1.06 65.4 Pa/m3/mol HISTORICAL REVIEW OF MTBE PRODUCTION PROCESS The MTBE plants actually consist of six units: Isomerization Unit (including deisobutanizer), Dehydrogenation Unit, MTBE Unit, Methanol Recovery Unit, Oxygenate Removal Unit and Olefin Saturation Unit. A common offsite utility system will be incorporated to distribute the required utilities to each unit. There are four method of producing MTBE implemented under license as the following: 1. UOP-Oleflex Process 2. Phillips STAR Process 3. ABB Lummus Catofin Process 4. Snamprogetti-Yarsingtez FBD (SP-Isoether) Process. 1.2.1 UOP-Oleflex Process 24
  25. 25. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR The UOP-Oleflex process uses multiple side-by-side, radial flow, moving-bed reactors connected in series. Preheated feed and interstage heaters supply the heat of reaction. The reaction is carried out over platinum supported on alumina, under near isothermal conditions. The catalyst system employs UOP's Continuous Catalyst Regeneration (CCR) technology. The bed of catalyst slowly flows concurrently with the reactants and is removed from the last reactor and regenerated in a separate section. The reconditioned catalyst is then returned to the top of the first reactor. processes involved are the deisobutenization, the isomerisation The typical and the dehydrogenation process that has been commercial in Malaysia. 1.2.2 Philips Star Process The second one is the Philips Steam Active Reforming (STAR) Process. The Phillips Steam Active Reforming (STAR) Process uses a noble metal-promoted zinc aluminate spinel catalyst in a fixed-bed reactor. The reaction is carried out with steam in tubes that are packed with catalyst and located in a furnace. The catalyst is a solid, particulate noble metal. Steam is added to the hydrocarbon feed to provide heat to the endothermic reaction, to suppress coke formation, and to increase the equilibrium conversion by lowering partial pressures of hydrogen and propane. 1.2.3 ABB Lummus Catofin Process The ABB Lummus Catofin Process uses a relatively inexpensive and durable chromium oxide–alumina as catalyst. This catalyst can be easily and rapidly regenerated under severe conditions without loss in activity. Dehydrogenation is carried out in the gas phase over fixed beds. Because the catalyst cokes up rapidly, five reactors are typically used. Two are on stream, while two are being regenerated and one is being purged. The reactors are cycled between the reaction and the reheat/regeneration modes, and the thermal inertia of the catalyst controls the cycle time, which is typically less than 10 minutes. The chromium catalyst is reduced from Cr6+ to Cr3+ during the dehydrogenation cycle. The raw materials used to produce MTBE by using this method are butanes, hydrogen and as well as recycled isobutene from the system itself. In this process, there is an isostripper column, which separates the heavies, and the light ends from which then could produce MTBE. 25
  26. 26. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 1.2.4 Snamprogetti-Yartsingtez FBD (SP-Isoether) The Snamprogetti-Yarsingtez SP-Isoether (FBD) Process uses a chromium catalyst in equipment, which is the fluidized bed that resembles conventional fluidized catalytic cracking technology used in the oil refinery. The catalyst is recirculated from the reactor to the regeneration section on a 30–60-min cycle. The process operates under low pressure and has a low-pressure drop and uniform temperature profile. Snamprogetti has been presenting and marketing their hydrogenation technology, ISOETHER 100, since 1997. This process is to be used to convert MTBE units by utilizing Snamprogetti’s MTBE Water Cooled Tubular Reactor Technology. In this SPIsoether Process, the products are MTBE and isooctagenas (iso octane gas). In this SP-Isoether Process the catalyst used in the isoetherification reactor is the same as those other typical processes, which is Platinum. (Please refer Appendix A – Figure 1.3). Four method processes of the MTBE above are favorable among the petrochemical firms. CHAPTER 2 PROCESS SELECTION 26
  27. 27. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Suitable process, which is gives a lot of profit and less problem is an important in order to determinant for the success of a plant. This chapter will briefly discuss the best process selected based on a few criteria. It covers general consideration, detailed consideration for process selection and conclusion on the process selection. 2.1 METHOD CONSIDERATION. From the processes mentioned earlier, there are many ways to produce MTBE. It is essential to choose the best method that will be used to produce MTBE. The selection of the method must consider the safety of the plant, minimum waste or by product generated, efficient and economical. Snamprogetti-Yarsingtez SP- Isoether FBD process will be chosen as the method to produce MTBE. More detailed reasons for the selection of this process are: High conversion (greater than 98 %) with few by-products compared to other process. From the economy aspect,Snamprogetti-Yarsingtez FBD Process can reduce the cost of setting up the plant as it can be implied in any of typical MTBE-produced plant, known as “Financial Safety Net”.(When an MTBE plant faces an oversupplied MTBE market, Isoether makes it possible to switch production from MTBE to a superior Alkylate.). As for the safety aspects of the plant, as the Snamprogetti-Yarsingtez FBD is a safe process as it just use the fluidize bed to the process of producing MTBE. The process operates under low pressure and has a lowpressure drop and this means that the fluidized bed is physically not harmful to anyone. As for the temperature, it operates under uniform temperature profile. As the temperature is not high, this means that the process is not as dangerous as other hightemperature-operated process. But, precautions should be taken seriously all the time, as we do not know when an accident could happen even in the safest place. As for the waste by using the Snamprogetti-Yarsingtez FBD Process, the product of the process is only MTBE and other effluent and as well as flue gas which are not harmful to the environment. Table 1.1 The comparison of the UOP-Oleflex, Philips Star, ABB Lummus Catofin and Snamprogetti- Yartsingtez SP-Isoether FBD process. 27
  28. 28. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Method and UOP-Oleflex STAR Philip ABB Lummus Snamprogetti- Consideration Process process Process Yarsingtez FBD Investment cost Investment cost Lower capital process Reduce the cost is very modest were evaluated investment of setting up the Economic for 700 BPSD plant as it can be Consideration (650tonne/day) implied in any of feed capacity typical MTBE- 97-99% 98% 99 .99% produced Greater than 98% 1. Higher per 1. The Stabilized 1.CD Tech 1.Environmental pass Product Is Near Efficiently Uses Friendly conversion and Equilibrium The Heat 2.”Financial at least 1-2% Mixture Of Released By An Safety Net”. higher catalyst Isobutane. Exothermic (When an MTBE selectivity as a 2.The Light-End Reaction. plant faces an result of lowest Yield Fr. Cracker 2.Conducting 2 oversupplied operating Is Less Than 1 Unit Operations MTBE market, pressure and Wt% Butane In 1 Equipment Isoether makes it temperature. Efficiency Feed (Isobutylene Selectivity) Advantages possible to switch 2. No catalyst production from losses. MTBE to a superior Alkylate.) Disadvantages 1. Less 1. Much heat is 1. The Reaction 1. Not widely efficiencies needed as Must Take Place practiced in furnace is used. In The Liquid industry, as it Phase –Catalyst needs thorough Must Remain research to Completely implement it. Wetted. 2.The Reaction Cannot Be Overly 28
  29. 29. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Endothermic 2.2.1 DETAILED PROCESS DESCRIPTION 2.2.2 Snamprogetti-Yartsingtez SP-Isoether (FBD) Process The Snamprogetti-Yarsingtez SP-Isoether (FBD) Process uses a chromium catalyst in equipment, which is the fluidized bed that resembles conventional fluidized catalytic cracking technology used in the oil refinery with 65% isobutane (i-C4H10) conversion to produce isobutene. Dehydrogenation reaction that occur in this process: iC4H10 iC4H8 + H2 The main feature of this process is that the catalyst filled annuli are connected in such a way that small, discrete amounts of catalyst can be withdrawn from the bottom of a reactor, and sent to the top of the reactor. Catalyst withdrawn from the bottom of the reactor is sent to a separate regeneration section for regeneration prior to being sent to the top of the reactor. The catalyst is recirculated from the reactor to the regeneration section on a 30–60-min cycle. The reactor and regeneration sections are totally independent of each other. The regeneration section can be stopped, even for several days, without interrupting the dehydrogenation process in the reactor section. The vaporized isobutane is fed along with fresh catalyst to the first, called reactor, and the spent catalyst is separated from the products and sent to the regenerator, where air (O 2) is added to oxidize the carbon. The reactor cracks the isobutane and forms coke on the catalyst. Then in the regenerator the coke is burned off and the catalyst is sent back into the reactor. The “magic” of this process is that the reactor-regenerator combination solves both the heat management and coking problems simultaneously. Burning off the coke is strongly exothermic, and this reaction in the regenerator supplies the heat (carried with the hot regenerated catalyst particles) for the endothermic cracking reactions in the reactor. The process operates under low pressure and has a low-pressure drop and uniform temperature profile. Products that have been produced from this unit are 29
  30. 30. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR isobutene. Isobutene available in the C4 stream from the Snamprogetti-Yarsintez FBD unit will be combining with methanol, which is sourced from the Sabah Gas Industries methanol plant in Labuan to produce, fuel-grade MTBE with a high-octane value in the MTBE unit. 2.2.3 MTBE Unit The MTBE unit includes two sections such as the main reaction section and the finishing reaction. In the main reaction section, 98% conversions of isobutene occurs mainly in the main reactor which are designed to provide the mechanical ands thermal conditions required by the expanded catalyst bid technology. Reactions occur in this unit are: 1. iC4H8 (isobutene) + CH3OH (methanol) 2. CH3OH + CH3OH (CH3)2O + H2O (DME) 3. iC4H8 + H2O C4H10O (TBA) C5H12O (MTBE) The reactor is operated in an up-flow direction with an external liquid recycle to remove the heat of reaction and to control the expansion of the catalyst bed. This selective reaction of methanol with isobutene is conducted in liquid phase at moderate temperature on an ion exchange resin type catalyst. The expansion of the catalyst bed in the reactor is ensured by pump around circulation loop with a cooling water cooler to control the reactor feed temperature to remove the heat of reaction. Resin traps on top of each reactor to trap resin in case of carryover with the liquid. In the finishing reactor section, isobutene final conversion is achieved in a catalytic column where reaction and distillation are performed simultaneously. 2.2.4 Distillation Column Unit 30
  31. 31. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR This column includes a separation column yielding MTBE product at the bottom and (isobutene, isobutene, normal butane, water and DME) with methanol entrained by azeotropy at the top. The reaction section bed is contained in the upper part of this column. An excess of methanol is maintained corresponding to the amount leaving the tower in the azeotrope. The required methanol is passed through guard beds and filtered prior to being charged to the catalytic column to achieve final conversion. Bottom MTBE product and the other by-product such as TBA, DME is sent to rundown tanks under level control after cooling in feed/bottom exchanger and trim cooler. The overhead of the column is condensed in the air-cooled condenser under pressure control. One part of the liquid is sent to the column as reflux and the other part to the liquid-liquid extraction unit after cooling. 2.2.5 Liquid-Liquid Extraction Unit In this unit methanol will extract from the isobutene, isobutene, normal butane to produce C4 raffinate from the overhead of the column and at the bottom, methanol and water are produced. C4 raffinate from this unit we decided to sell to the Korea. CHAPTER 3 ECONOMIC SURVEY 31
  32. 32. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.1 MARKET SURVEY 3.1.1 World Market The MTBE market has been in strong continuous growth since 1992. For instance, the 1998 world consumption was approximately 19.5 million tonnes, about double that of 1992, representing an annual growth rate of about 12%. Present trends indicate a mild growth in 2000, up to 20 million tonnes, with US consumption slightly declining and other parts of the world growing (EEA 2000). The MTBE’s role in U.S. gasoline grew rapidly through 1995 given away in figure 3.1. Figure 3.1 MTBE’s role in U.S. gasoline grew rapidly through 1995 (Sources: Local Issues, Global Implications) 3.2 ASIA MARKET Most Asia countries such as South Korea, Japan, Hong Kong, Taiwan, China, Malaysia, Singapore, Philippines and Thailand, have already phased lead out of their gasoline pool and are replacing it with oxygenates such as MTBE. Due to MTBE’s relative ease in blending into gasoline, easy transportation and storage, as well as relatively cheap and abundant supply, MTBE is the most widly use oxygenate in Asia. However, the use of MTBE in gasoline blending is not mandatory for countries like South Korea and Thailand. South Korea, for instance, requires a 1.3% - 2.3% 32
  33. 33. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR oxygenate content in gasoline during the winter, compared to a minimum of 0.5% for the summer. In other Asian Countries, MTBE is mainly use as an octane booster to replace lead. (source: features mtbe asias.html). 3.3 DEMAND World demand of MTBE mod scenario is about 4.1 mil ton per annum consumption in US West Coast at stake due to the legislation from 1998 to 2010. It has as an impact on 80% of PETRONAS MTBE exports to the US. This mod scenario is representing in figure 3.2. Figure 3.2: World MTBE demand (1998-2010) – mod scenario (Sources: Petronas’s Library Kuala Lumpur City Center (KLCC) U.S. demand is about 250,000b/d, dominates MTBE consumption. Most MTBE is used to comply with mandated oxygen content rules for gasoline supplied to either RFG or wintertime carbon monoxide areas. A small amount may be utilized for octane enhancement. In Europe, MTBE demand is estimated about 60,000 b/d. MTBE use in Europe is essentially confined to Octane enhancement, and about 6,000 b/d is exported to the United States. Eastern Europe currently consumed about 10,000 b/d of MTBE. In Asia, demand for MTBE in this region is expected to grow at much more rapid rate than elsewhere in the world. The rate will taper off late in decade from about 12% per year to about 8% by the turn of the century, since the early rapid growth has 33
  34. 34. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR been fed by the lead phase down which should be nearly complete by 2000. Throughout the period, the region will be a net importer of MTBE, mostly obtained from the Middle East. The trade balance of MTBE in Asia and Pacific is expected to be in table 3.1. (Sources: MTBE annual Report) Table 3.1 Trade Balance of MTBE in Asia and Pacific (Sources: MTBE annual Report) Capacities listed are the average available during the year. Details for 1995 and 1999 of MTBE Balance for Asia and Pacific are shown in table 3.2. These data are also shown graphically in figure 3.3 which indicate for MTBE supply and demand Asia and Pacific. (Sources: MTBE annual Report) Table 3.2: MTBE Balance for Asia and Pacific (Sources: MTBE annual Report) 34
  35. 35. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR MTBE supply and demand Asia and Pacific Figure 3.3: MTBE supply and demand Asia and Pacific (Sources: MTBE annual Report) Demand for MTBE expected to be marginally firmer in the near future as Asian Countries such as Indonesia and India are working totally phase out lead from their gasoline pool. Supply on other hand is expected to remain abundant, as Asia is able to produce about 3 million Mt/yr of MTBE for its Captive consumption. In addition to this, Asia attracts a regular supply of about 500,000 ton/yr of MTBE from Middle Eastern and Europe sources.(Reference: features mtbe asias.html). 35
  36. 36. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.4 PRODUCTION CAPACITY Commercial production of MTBE started in Europe in 1973 and in the US in 1979. Total worldwide production capacity in 1998 was 23.5 million tones and the actual production was 18 million tones The annual production volume of MTBE in the year 2000 in the Europe was 2,844,000 tons. About 129,000 tonnes was imported and about 479 000 tonnes were exported outside the Europe in the year 2000 ((Dewitt & Company Inc. 2002). The majority of the exported volume (> 83%) was exported to USA and Canada. The majority of exported volume (> 80%) was transported as non-blended MTBE and minority as a component of petrol (blended). The annual consumption of MTBE within the Europe was hence 2,495,000 tons in the year 2000 (see table below). For the future no substantial increase in MTBE usage is expected. (Dewitt & Company Inc. 2002). Table 3.3: Production, import, export and consumption in Europe in year 2000 (tonnes/year) souces: (Dewitt & Company Inc. 2002). Production 2 844 000 Import into Europe 129 000 Export outside Europe 479 000 Consumption 2 495 000 The world's MTBE industry today is operating at about 80% of capacity. The US is by far the largest market, having about 43% of the production capacity but consuming 63% of total global output. On stability, the Middle East is the swing producer, exporting more than 50,000 bbl/day to the US and elsewhere. 3.5 SUPPLY DeWitt’s Company estimates for local production of MTBE a summarized in table 3.4. Most of plants unit are refinery-based units taking isobutylene from FCCU units, or as Raffinate I from olefins plants. Since olefin plants in the region a mostly naphthabased, they produce significant quantities of C4 olefins for this purpose. There is one butane-based plant in Malaysia. Table 3.4 also shown for MTBE plants suppliers to Asia and Pacific. 36
  37. 37. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Table 3.4 Suppliers MTBE plant in Asia and Pacific (Sources: MTBE annual Report) 3.6 MARKET PRICE 3.6.1 Methanol Price of methanol, as feedstock in Asia is $240 - $280 /ton. While in Europe, the prices is $265 - $270 / ton free on board (fob) Rotterdam. In U.S. the price of methanol is 76 cts – 77cts/ gal in fob. Global Methanol demand is expected to increase to 3.5 % per year over the next 5 years, compared to 1.0% - 1.5% growth in 2002 and 2003. Those lower growth rates are attributable to the phase-out of Methyl tert-butyl ether (MTBE) as oxygenate in gasoline in California, and slower economic growth in China caused by SARS. Methanol growth in China is forecast at 7% - 8.5% per year, fueled by formaldehyde and acetic acid demand. (Chemicals Week) 3.6.2 Isobutane Standard price for isobutene is stated by followed: 37
  38. 38. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Table 3.5 : Standard price for isobutane Grade Purity Grade 4.0 99.99% Grade 3.0 99.9% Instrument 99.5% 3.6.3 Cylinder Size LP30 LP15 LP05 LP01 1/2 Ton LP30 LP15 LP05 LP01 1 Ton LP30 LP15 LP05 LP01 Volume lbs 117 60 23 6 490 117 60 23 6 490 117 60 23 6 Price per Cylinder RM900.00 RM600.00 RM370.00 RM200.00 RM1225.00 RM380.00 RM240.00 RM170.00 RM100.00 RM890.00 RM293.00 RM185.00 RM100.00 RM75.00 Catalyst Price of Chromia catalyst Compound – USD60 000/Rottedam (Rdam) from the existing plant. (En Mohd. Napis, from MTBE plant, Gebeng ) 3.6.4 Conclusion Our company will import the methanol and isobutane as feedstock, from Petronas Malaysia and United State (US) respectively. Methanol feedstock will be supplied from Gurun, Kedah production capacity of 66,000 ton/year. For the second feedstock, isobutane (instrument grade) will be supplied by Chevron Phillips Chemical Company LP, 10001 Six Pines Drive, The Woodlands, Texas, US by shipping method. MTBE is suitable as a gasoline additive which simultaneously increases the octane rating of the fuel and adds oxygen which promotes cleaner burning. When used in place of lead-based octane enhancers, dual environmental benefits are realized, a reduction in atmospheric lead concentrations and reduced emissions of carbon monoxide and other smog forming chemicals. Since the 1970s, the worldwide 38
  39. 39. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR consumption of MTBE has increased significantly and many new facilities have been constructed to support the growing market (Kirschner, 1996; Riddle, 1996). MTBE production will increase in future in Asia, Asia Pacific, Middle East and Europe even though MTBE is banned in California but not in the entire nation of the United States. 3.7 ECONOMIC ANALYSIS An economic analysis used to smooth the progress of based on existing plant. This analysis is important to ensure that the chemical plants converge and the economics is satisfactory before the plant operate. All the data taken from MTBE Annual 1994, DeWitt & Company Incorporated, 16800 Greenpoint Park, Suite 120 N, Houston, Texas, that given by Petronas Library, KLCC. 3.7.1 Break-Even Analysis When chemical engineers determine outlay for any type commercial process, they want these costs to be enough accuracy to provide reliable decision. To accomplish this, they must have a complete understanding of the many factors that can affect costs. Break-even analysis is important to ensure that the plant can give profit before the plant can run. The objective of break even analysis is to find the point, in dollars or in ringgits and units, at which costs equal revenues. This point is the break even point. Break even analysis requires an estimation of fixed costs, variable costs and revenue. Fixed costs are costs that continue even if no units are produced. Examples include depreciation, taxes, debt, and mortgage payments. Variable costs are those that vary with the volume units produced. The major components of variable costs are labor and materials. However, others cost, such as the portion of the utilities that varies with volume, are also variable cost. The different between selling price and variable cost is contribution. Only when total contribution exceeds total fixed cost will there be profit. 39
  40. 40. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Another element in break-even analysis is the revenue function. From the graph, revenue begins at the origin and proceeds upward to the right, increasing by selling price of each unit. Where the revenue function crosses the total cost line (the sum of fixed and variable costs), is the break even point, with a profit corridor to the right and a loss corridors to the left. Table 3.6: Cost of producing MTBE 500,000 ton/year (Sources: DeWitt & Company Incorporated, Annual Report) Table 3.6 showed that the cost of production of MTBE based on existing plant producing 500,000 ton/year. From table 3.6, given data, break-even analysis can be calculated to know the break-even point figure. Figure below indicate that break-even chart, where it has been calculated by using excel that shown in table 3.8 and based on the data given from table 3.6. 40
  41. 41. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Figure 3.4 : Break even analysis chart calculated by using excel. From the break even chart figure above, the value of break-even point at the existing capacity of 500,000 ton/year is 185,629.85 tons in units and RM 244,679,817.14 in Ringgit Malaysia (RM). This value indicates the minimum units and values needed to be sold. The given capacity of 500,000 tons/year can give profit to the company. The margin of safety (MOS) calculated from the graph, which is 314,370.15 tons and RM414,373,182.86. Margin of safety (MOS) in percentage of sales is 62.87%. The sale is allowed to drop about 62.87% before the company will incurred a loss. In other word, at selling 300,000 tons/year capacity will also give profit to our company. The margin of safety from the graph for 300,000 ton/year calculated is 114,370.15 tons and RM150,751,982.86. The margin of safety (MOS) as percentage of sales is 38.12%. The sale is allowed to drop about 38.12% before the company will incurred a loss. All the data calculation is shown in the next section. 41
  42. 42. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 3.7.2 Data Calculation All the data based on 500,000 tons/year producing MTBE from existing plant. Table 3.7 Values in USD converted to RM (Sources: Data collected from table 3.6) Total revenue, TR Total variable cost, TVC Total fixed cost, TFC RM 659,053,000.00 RM 504,754,000.00 RM 57,285,000.00 Total Revenue (TR), MTBE (500,000 ton), TR = Quantity of MTBE X Price of MTBE = QMTBE X PMTBE = 500,000 tons X USD346.87 X 3.8 = RM 659,053,000 Total cost TC = total fixed cost + total variable cost = TFC + TVC Where, Total fixed cost = 500,000 ton X USD30.13 X 3.8 = RM 57,285,000.00 Total variable cost = 500,000 ton X USD (226.4 + 39.26) X 3.8 = RM 504,754,000.00 ∴ Total cost, TC = RM57,285,000.00 + RM 504,754,000.00 = RM 562,039,000.00 Tables 3.7 represent cost per unit ton converted into Ringgit Malaysia (RM), taking data’s directly from the table 3.6. Table 3.8 Values in USD converted to RM per ton (Sources: Data collected from table 3.6) Revenue (RM) per ton RM1,318.00 Variable cost (RM) per ton RM 1,009.51 Fixed cost (RM) per ton RM114.57 Break-even point in ton can be calculated based on formula equation, which given by follow: 42
  43. 43. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Break-even point, BEP (tons) = Total Fixed cost Contribution/ton where, Contribution/ton = revenue / ton - variable cost / ton ∴ BEP (tons) = ______RM 57,285,000.00_____ (RM1, 318.00 - RM 1,009.51) = 185,629.85 tons (the minimum capacity) Next, Break-even point in RM can be calculated based on formula equation, which given by follow: ∴ BEP (RM) = Break-even point, BEP (tons) X revenue / ton = 185,629.85 tons X RM1, 318.00 = RM 244,679,817.14 Beside that, margin of safety and percentage of sale can be calculated as follows: For 500,000 ton/year production, ∴ Margin of safety (MOS) in units = Budgeted sale (units) - BEP (units) = 500,000 tons - 185,629.85 tons = 314,370.15 tons ∴ Margin of safety (MOS) in RM = Budgeted sale (RM) - BEP (RM) = RM 659,053,000.00 - RM 244,679,817.14 = RM 414,373,182.86 ∴ Margin of safety (MOS) as percentage of sales = MOS (RM) x 100% Sales(RM) = RM 414,373,182.86 x 100% RM 659,053,000 = 62.87% 43
  44. 44. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR For 300,000 ton/year production, ∴ Margin of safety (MOS) in units = Budgeted sale (units) - BEP (units) = 300,000 tons - 185,629.85 tons = 114,370.15 tons ∴ Margin of safety (MOS) in RM = Budgeted sale (RM) - BEP (RM) = RM 395,431,800 - RM 244,679,817.14 = RM 150,751,982.86 ∴ Margin of safety (MOS) as percentage of sales = MOS (RM) x 100% Sales(RM) = RM150,751,982.86 x 100% RM 395,431,800 = 38.12% Table 3.9 shown that the calculation of break-even point by using excel. Table 3.9: Data calculation by using excel in RM (Sources: Data taking from table 3.7) 44
  45. 45. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CAPACITY TFC1 0 57,285,000.00 10000 57,285,000.00 20000 TVC1 0 TR1 TC1 0 57,285,000.00 10,095,080.00 13,181,060 67,380,080.00 57,285,000.00 20,190,160.00 26,362,120 77,475,160.00 40000 57,285,000.00 40,380,320.00 52,724,240 97,665,320.00 60000 57,285,000.00 60,570,480.00 79,086,360 117,855,480.00 80000 57,285,000.00 80,760,640.00 105,448,480 138,045,640.00 100000 57,285,000.00 100,950,800.00 131,810,600 158,235,800.00 120000 57,285,000.00 121,140,960.00 158,172,720 178,425,960.00 140000 57,285,000.00 141,331,120.00 184,534,840 198,616,120.00 160000 57,285,000.00 161,521,280.00 210,896,960 218,806,280.00 180000 57,285,000.00 181,711,440.00 237,259,080 238,996,440.00 200000 57,285,000.00 201,901,600.00 263,621,200 259,186,600.00 220000 57,285,000.00 222,091,760.00 289,983,320 279,376,760.00 240000 57,285,000.00 242,281,920.00 316,345,440 299,566,920.00 260000 57,285,000.00 262,472,080.00 342,707,560 319,757,080.00 280000 57,285,000.00 282,662,240.00 369,069,680 339,947,240.00 300000 57,285,000.00 302,852,400.00 395,431,800 360,137,400.00 320000 57,285,000.00 323,042,560.00 421,793,920 380,327,560.00 340000 57,285,000.00 343,232,720.00 448,156,040 400,517,720.00 360000 57,285,000.00 363,422,880.00 474,518,160 420,707,880.00 380000 57,285,000.00 383,613,040.00 500,880,280 440,898,040.00 400000 57,285,000.00 403,803,200.00 527,242,400 461,088,200.00 420000 57,285,000.00 423,993,360.00 553,604,520 481,278,360.00 440000 57,285,000.00 444,183,520.00 579,966,640 501,468,520.00 460000 57,285,000.00 464,373,680.00 606,328,760 521,658,680.00 480000 57,285,000.00 484,563,840.00 632,690,880 541,848,840.00 500000 57,285,000.00 504,754,000.00 659,053,000 562,039,000.00 CHAPTER 4 45
  46. 46. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR PLANT LOCATIONS AND SITE SELECTION 4.1 PLANT LOCATION The location of the plant can have a crucial effect on the profitability of a project and the scope for future expansion. Many factors must be considered when selecting a suitable site. A good location is required to optimise the production of the plant. It is important to know that, not all Malaysian industrial park caters the need of a chemical plant. Also not all industrial park allows the building of chemical plants. Our industrial parks are divided into categories such as: 1. Light industrial 2. Medium industrial 3. Heavy industrial 4. General industrial 5. Hi-tech industrial 4.2 GENERAL CONSIDERATION ON THE SITE SELECTION All the information about plant locations are based on the data gathered from the Malaysian Industrial Development Authority (MIDA). And we refer detail information on important factors that need to be considered in the site selection. In the process of selecting the location, we did some evaluation. Among the principle factors considered are: 4.2.1 Location With Respect To Marketing Area For materil that are produced in bulk quantities, such as cement, fertilizer, raw material of petrochemical product, where the cost of product per tone is relatively low and the cost of transport a significant fraction of the sales price, the plant must located close to the primary market. This consideration will be less important for low volume production, high priced products; such as pharmaceuticals, plastisizer and etc. in an international 46
  47. 47. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR market, there may be an advantage to be gained by locating the plant within an area with preferential tariff agreement. 4.2.2 Raw Material Supply The availability and price of suitable raw materials will often determine the site location. Plant producing bulk chemicals are best located close to the source of the major raw material, where this is also close to the marketing area. 4.2.3 Transport Facilities The transport of materials and products to and from the plant will be an overriding consideration in site selection. If practicable, a site that we are consider that close to at least two major forms of transport: road, rail, waterway or a sea port. Road transport being increasing used, and is suitable for local distribution from central warehouse. Rail transport will be cheaper for the long distance transport of bulk chemicals . Air transport is convenient and efficient for the movement of personnel and essential equipment and supplies and the proximity of the site to a major airport also considered. 4.2.4 Availability of Labour Labour that will be needed for construction of the plant and its operation. Skilled construction workers will usually be brought in from outside the site area, but there should be an adequate pool of unskilled labour available locally and labour suitable for training to operate the plant. Skill tradesman will be needed for plant maintenance. Local trade union customs and restrictive practices will have to be considered when assessing the availability and suitability of the local labour for requirement and training . 4.2.5 Availability of Utilities 47
  48. 48. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Chemical processes invariably require large quantities of water for cooling and general process used and the plant must be located near a source of water of suitable quality. Process water may be drawn from a river, wells or purchased from a local authority. At some site, the cooling water required can be taken from a river or lake or from the sea; at other locations cooling towers will be needed. Electrical power will be needed at all sites. Electrochemical processes that required large quantities of power: for example, aluminium smelters need to be located close to a cheap source of power. A competitively priced fuel must be available onsite for steam and power generation. 4.2.6 Environmental Impact and Effluent Disposal All industrial processes produce waste products and full consideration must be given to the difficulties and cost of their disposal. The disposal of toxic and harmful effluents will be covered by local regulations and the appropriate authorities must be consulted during the initial site survey to determine the standards that must be met. An environmental impact assessment should be made for each new project or major modification of addition to an existing process. 4.2.7 Local Community Considerations The proposed plant must fit in with and be acceptable to the local community. Full consideration must be given to the safe location of the plant so that it does not impose a significant additional risk to the community. On a new side, the local community must be able to provide adequate facilities for the plant personnel: schools, banks, housing and recreational and cultural facilities. 4.2.8 Land (site consideration) 48
  49. 49. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Sufficient suitable land must be available for the proposed plant for future expansion. The land should ideally be flat, well drained suitable load-bearing characteristics. A full site evaluation should be made to determine the need for piling or other special foundations. 4.2.9 Political and Strategic Considerations Capital grants, tax concessions and other inducements are often given by government to direct new investment to preferred locations such as areas of high unemployment. The availability of such grants can be the overriding factor in site selection. 4.3 OVERVIEW ON PROSPECTIVE LOCATIONS Our process is a petrochemical base process; therefore we choose to locate our plant in a petrochemical complex. The reason is quite simple; a petrochemical complex could simplify the formation and the maintenance of a chemical plant. It could also cut the daily operation cost and saving us the hassle of transportation. In Malaysia there are only three such places, known as the Integrated Petrochemical Complexes. These complexes are situated in each of the site below: 1. Telok Kalong Industrial Park. 2. Tanjung Langsat Industrial Park. 3. Bintulu Industrial Park. Other than the above factors, the capacity of plant was also taken into consideration in determining the suitability of site. Plant capacity will determine how big the space required to build the plant and the storage area and also the mode of transportation to be use. The manufacture of MTBE is classified as a petrochemical project. Several locations of industrial area particular at Teluk Kalong Industrial Area in Terengganu, Tanjung Langsat Industrial Area in Johor and Bintulu Industrial Area, Sarawak that we are refer for location. 49
  50. 50. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 4.3.1 Teluk Kalong Teluk Kalong Industrial Estate located 9.6 km from Kemaman. Total area available 167.46 hectares. The price of land in ranges RM 0.46 to RM 4.18 per Feet Square. This area is proposed for petrochemical and heavy industry petrochemical. The Electricity is generated at the following station. Total generation capacity is 900 MW. Local consumption is less than 1/3. No major breakdown, low frequency of interruption. Water most plentiful with surplus capacity. Water supply capacity at various treatment plants total 331000-meter cube per day, with planned upgrading for additional requirement. Kenyir Lake with 39000 hectares of water with 134 metre average depth, make Terengganu a potential export of water middle East. Water supply is in Bukit Shah. Water tariffs (industrial) are RM1.15 metre cube. The raw materials supplier of isobutene is availability from Chevron Philips Chemical Company LP, United State and methanol is availability from Petronas Malaysia, Labuan. 1. • Airport facilities Terengganu major industrial locations are serve by 3 airports - Kuantan - Kerteh - Kuala Teregganu • 2. • 4.3.2 Kuala Teregganu Port Facilities Kemaman Port, Kerteh Port and Kuantan Port Tanjung Langsat Industrial Park Tanjung Langsat is designed as hub for heavy/medium industries with all the necessary infrastructure and service facilities. 91.43 km distance from Johor Baharu. The infrastructure works such as the Pasir Gudang – Segamat Highway. Sungai Johore Bridge and dedicated Port in Tanjung Langsat. Tanjung Langsat Industrial Complex is a sprawling area just a stone’s through from Pasir Gudang Industrial Area. A total hectare still available is 1,085.95. Selling price is RM8 to RM22 square feet. In term of seaport two seaports are currently being constructed at Tanjung Pelepas, 50
  51. 51. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR located 40 km west of Johore Baharu city and Tanjung Langsat located 10 km east of the Johore Port. Tenaga Nasianal Berhad (TNB) provides electricity. Two airports in the 50km radius. There is the Sultan Ismail International Airport (common known locally as Senai Airport) in Johore Baharu and the Changi International Airport in Singapore. The Sultan Ismail International Airport, which is located about 30km to the north west of JB city, is currently being expended and upgrades to become the regional airport for southern peninsular Malaysia. 4.3.3 Bintulu The distance from nearest town is 224.29 km from Sibu. Type of industries is light and medium petrochemical. Area available is 77 hectares. Selling price RM2.5 to RM10 per feet square. Electricity supplies by Sarawak Electricity Supply Cooperation (SESCO). • Airport facilities - Bintulu Airport • Port Facilities - Bintulu Port 51
  52. 52. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Table 4.1 The Comparison of The Potential Site Location: Teluk Kalong Industrial Park Tanjung Langsat Industrial Park Bintulu Industrial Park 9.6 km from Kemaman 91.43 km from Johor Baharu 224.29 km from Sibu Types of Industry Isobutane from US and methanol from Labuan Petrochemical and heavy industry Isobutane from US and methanol from Labuan Petrochemical light and medium Isobutane from US and methanol from Labuan Petrochemical light and medium Area Available 167.46 hectares 1085.98 hectares 77 hectares RM 0.46 - 4.18 RM 8.00 - 22.00 RM 2.50 - 10.00 Electricity Supply Tenaga National Berhad Tenaga National Berhad Sarawak Electrycity Supply Cooperation (SESCO) Water Supply Bukit Shah Water Treatment Road Facilities Kuala TerengganuKuantan-Kuala LumpurKuala Terengganu-KertehTeluk Kalong-KuantanKuala Lumpur Distance from the nearest town Raw Material Land Price 2 (RM/ft ) Airport Facilities Port Facilities Water Tariffs 3 (RM/m ) Kuala Terengganu Airport Kerteh Airport Kemaman Port, Kerteh Port Kuantan Port RM 1.15 Syarikat Air Johor and Logi Air Sg. Layang Syarikat Air Sarawak North-South Highway from Bukit Kayu Hitam to Singapore- Major Road : Bintulu Sibu and Bintulu - Miri Senai International Airport Bintulu Airport Pasir Gudang Port Bintulu Port RM 1.68 (0-20 m 3) RM2.24 (more than 20 m 3) RM 0.95 (0 -25 m 3) RM1.20 (more than 25 m 3) (Source: MIDA) A few proposed plant sites were narrowed down based on the above factors (table 4.2). Table 4.2 is a summary of location and factors being considered. After detailed study of 52
  53. 53. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR the factors, each was given weightage and was estimated. The result tabulated in table 4.2 for the purpose of comparison. Table 4.2 The Comparison of Location in term of Weightage Study Weightage Telok Kalong Industrial Area Tanjung Langsat Industrial Area Bintulu Industrial Area Marketing Area 10 8 7 7 Raw Material 10 8 9 9 Transport 10 8 7 6 Availabillity of Labour 10 8 8 7 Utilities 10 8 9 7 Total Land Available 10 8 9 8 Climate 10 9 9 9 Price of Land 10 9 5 7 Local Community Consideration 10 6 8 9 Incentives 10 8 8 8 TOTAL 100 80 79 77 ∴ 0 to 10 with 10 is the best Table 4.3 The Electricity Tariffs (Industrial Tariff) for Peninsular Malaysia and Sarawak 53
  54. 54. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Tariff Peninsular Malaysia Tariff D (Low Voltage, and less than 6.6 supply) for all consumptions Cost per kWh kV Tariff E1 (Medium Voltage General, 6.6 kV - 66 kV supply) for all consumptions. For each kW of maximum demand per month: RM 17.30 25.8 19.8. Tariff E2 (Medium Voltage Peak/Off-Peak, 6.6 kV 66kV supply) Peak period (0800-2200 hours), 20.8 Off-Peak period (2200-0800 hours). 12.8 For each kW of maximum demand per month during peak period: RM21.70 Tariff E3 (High Voltage Peak/Off-Peak, more than 132 kV supply) Peak period (0800 -2200 hours), Off-Peak period (2200 - 0800) hours). For each kW of maximum demand per month during peak period: RM 20.80 Sarawak Tariff 11 1st 100kWh In excess of 100kWh to 3000 kWh In excess of 3000 kWh Minimum charge per month: RM 10.00 Tariff 12 All units 17.8 10.8 40 30 21 17 For each kW of maximum demand per month: RM12.00 Minimum charge : RM 12.00 per kW x billing demand Tariff 13 (Peak/Off-Peak) Peak period ( 0700 - 2400 hours) Off-Peak period ( 0000 - 0700 hours) For each kW of maximum demand per month during peak period: RM20.00 Minimum charge: RM 20.00 per kW x billing demand. 17 10 (Source: MIDA) 54
  55. 55. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 4.4 CONCLUSION Based on the factor weightage studied, it can be concluded that Telok Kalong Industrial Estate is the most suitable and practical location to choose as a site for MTBE plant. The philosophy of in situ consumption of much of the production MTBE, together with remaining product aimed directly at the export market and also makes the need for port facilities of paramount importance. The Tanjung Langsat and Bintulu Industrial Area are not impressive for MTBE plant. There are many other reasons influences our decision including: • Nearest of the Kuantan Port, Kemaman Port and Kerteh Port facilities is more convenient and economically for export and import purposes. • Excellent and consistent support from bulky oil, gas and chemical supplier from Kerteh. Constantly upgrading existing and developing new infrastructure, facilities and supporting industries. These include the construction of roads; to increase accessibility to and from the estates are scheduled. 55
  56. 56. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CHAPTER 5 ENVIRONMENTAL CONSIDERATION 5.1 INTRODUCTION Nowadays, environmental issues become very important. Besides this, a good waste treatment system is also important in order to reduce and minimize environmental pollutants. The chemical waste in the form of solid, liquid and gases must be treated before being discharged into sewage, drain and atmospheres. Any chemical plant to be set up in Malaysia must follow the rules and regulations under the Department of Environment (DOE) Malaysia, which includes the Environmental Quality Act 1974. Under Environmental Quality Act (Sewage and Industrial Effluents) Regulation 1979 and Environment Quality Act (Clean Air) 1978. The plant owner or waste generator must ensure that waste generated disposed appropriately to prevent environmental pollution. The proper and suitable methods should be implemented in dealing with the waste disposal. Kualiti Alam Sdn. Bhd is one of the licensed contractors specialized in the industrial waste disposal in Malaysia. MTBE plant is not excluded from these regulations. As our plant produces MTBE and other byproducts like raffinate but generally they are not hazardous to the environment and human if safety measures are taken into consideration. These environmental considerations depend on the location of our plant. The plant will follow the Standard B of water quality measurement and also need some waste treatment facilities to minimize the pollution from our plant. 56
  57. 57. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR STACK GASES Gas Emission Treatment Direct flame combustion was used to burn the excess gas. Flare is usually open ended combustion unit. Therefore, the combustion process will be controlled by flow rate of gases mixture to prevent incomplete combustion. Another treatment is thermal combustion. It is an incinerator used in the cases where the concentration of combustible gases is too low to make direct flame incineration insufficient condition. The temperature of operation depends upon the type of pollutant in waste gas. Thermal combustion must be carefully designed to provide safe, efficient operation and to prevent incomplete combustion. Time, temperature, and oxygen must be carefully monitored. (Howard et. al 1985) Stack gas means the product of combustion process usually occur at machine or generator. It is usually the fuels used occurred in the complete combustion process, but it produced unwanted gas such as carbon monoxide, sulphur oxide and other gases. In our MTBE plant, the stack gases is only Hydrogen and it is stored in a special tank before being sold to interested company at market price. 5.3 5.3.1 WASTEWATER TREATMENT Wastewater Characteristics Wastewater characteristics vary widely from industry to industry. Obviously, the specific characteristics will affect the treatment techniques chosen for use in meeting discharge requirements. Because of the large number of pollutant substances, wastewater characteristics are not usually considered on a substance-by-substance basis. Rather, substances of similar pollution effects are grouped together into classes of pollutants or characteristics are indicated below. 5.3.1(a) Priority Pollutants 57
  58. 58. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Recently, greatest concern has been for this class of substances for the reasons given previously. These materials are treated on an individual-substance basis for regulatory control. Thus each industry could receive a discharge permit that lists an acceptable level for each priority pollutant. 5.3.1(b) Organics The organic composition of industrial wastes varies widely, primarily due to the different raw materials used by each specific industry. These organics include proteins, carbohydrates, fats and oils, petrochemicals, solvents, pharmaceutical, small and large molecules, solids, and liquids. Another compilation is that a typical industry produces many diverse waste streams. Good practice is to conduct a material balance throughout an entire production facility. This survey should include a flow diagram, location and sizes of piping, tanks, and flow volumes, as well as an analysis of each stream. An important measure of the waste organic strength is the 5-day biochemical oxygen demand (BOD5). As this test measures the demand for oxygen in the water environment caused by organics released by industry and municipalities, it has been the primary parameter in determining the strength and effects of a pollutant. This test determines the oxygen demand of a waste exposed to biological organisms (controlled seed) for an incubation period of five days. Usually this demand is caused by degradation of organics according to the following simplified equation, but reduced inorganics in some industries may also cause demand (i.e., Fe2+, S2- and SO32-). Organic waste + O2 CO2 +H2O In general, low-molecular-weight water-soluble organics are biodegraded readily. As organic complexity increases, solubility and biodegrability decrease. Soluble organics are metabolized more easily than insoluble organics. Complex carbohydrates, proteins and fats and oils must be hydrolyzed to simple sugars, aminos, and other organics acids prior to metabolism. Petrochemicals, pulp and paper, slaughterhouse, 58
  59. 59. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR brewery, and numerous other industrial wastes containing complex organics have been satisfactorily treated biologically, but proper testing and evaluation is necessary. 5.3.1(c) Inorganics The inorganics is most industrial wastes are the direct result or inorganic compounds in the carriage water. Soft-water sources will have lower inorganics than hard-water or saltwater sources. However, some industrial wastewaters can contain significant quantities of inorganics which result from chemical additions during plant operation. Many food processing wastewaters are high in sodium. While domestic wastewaters have a balance in organics and inorganics, many process wastewaters from industry are deficient in specific inorganic compounds. Biodegration of organic compounds requires adequate nitrogen, phosphorus, iron, and trace salts. Ammonium salts or nitrate salts can provide the nitrogen, while phosphates supply the phosphorus. 5.3.1(d) pH and Alkalinity Wastewaters should have pH values between 6 and 9 for minimum impact on the environment. Wastewaters with pH values less than 6 will tend to be corrosive as a result of the excess hydrogen ions. On the other hand, raising the pH above 9 will cause some of the metal ions to precipitate as carbonates or as hydroxides at higher pH levels. Alkalinity is important in keeping Ph values at the right levels. Bicarbonate alkalinity is the primary buffer in wastewaters. It is important to have adequate alkalinity to neutralize the acid waste components as well as those formed by partial metabolism or organics. Many neutral organics such as carbohydrates, aldehydes, ketones, and alcohols are biodegraded through organics acids which must be neutralized by the available alkalinity. If alkalinity is inadequate, sodium carbonate is a better form to add than lime. Lime tends to be hard to control accurately and results in high pH levels and precipitation of the calcium which forms part of the alkalinity. In a few instances, sodium bicarbonate may be the best source of alkalinity. 59
  60. 60. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 5.3.1(e) Temperature Most industrial wastes tend to be on the warm side. For the most part, temperature is not a critical issue below 37oC if wastewaters are to receive biological treatment. It is possible to operate thermophilic biological wastewater-treatment systems up to 65oC with acclimated microbes. Low-temperature operations in northern climates can result in very low winter temperatures and slow reaction rates for both biological treatment systems and chemical treatment systems. Increased viscosity of wastewaters at low temperatures makes solid separation more difficult. Increased viscosity of wastewaters at low temperatures makes solid separation more difficult. Efforts are generally made to keep operating temperatures between 10 and 30oC if possible. 5.3.2 Liquid Waste Treatment 5.3.2(a) Equalization Treatment Liquid treatment generally is necessary in any plant. In our plant, we also have liquid treatment but in general, we only state the general method, as our plant does not produce any significant liquid waste. In any liquid waste treatment, we need equalization treatment. The equalization treatment is an initial procedure in liquid waste treatment. The purpose of equalization is to minimize and control the fluctuation in liquid waste characteristic. Besides it provides the suitable and optimum condition for biological and chemical treatment. It also provides adequate damping to minimize the chemical consumption. The procedure will occur in the equalization tank. The size of tank and time of equalization process depend on the liquid waste amount. The Activated Sludge process will be used for this treatment. It is carried out in Aerobic condition. The main purpose of activated sludge process is to remove soluble and insoluble organic matter that converted into flocculants microbial suspension and settable microbial. It also permits the use of gravitational solid liquid separation technique for the above requirement. The organic matter where measured in the form of BOD and COD serves as food and energy source for microbial growth. It converts the pollutant into microbial cell 60
  61. 61. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR and oxidized end product such as CO2 and H2O by microbial activities. Therefore, Submersible Aerator as mixing device will supply the oxygen and nutrient into aeration tank and therefore improves the quality of the liquid. (Howard et. al, 1985) 5.3.2(b) Solid Waste Treatment The solid waste treatment will be minimized by regenerating the catalyst. Regeneration processes depend on the characteristic of catalyst after whole reaction. Licensed contractor will dispose the solid waste to follow the DOE regulation. By the way, the scheduled maintenance activities will be implemented. Dewatering system will be used to solidify and extract the catalyst. Therefore, clarifier and filter press were used in these treatments. Clarifier is used to clarify any impurities before going through the filters. The size of equipment depends on the flow rate and holding time of these processes. Maintenance activities will be scheduled based on the availability of workers and machines. Skilled and experienced workers will do the maintenance activities, (Bailed, 1995). 61
  62. 62. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Industrial Process Waste Reduction Waste Generation Re-use Storage Transfer/ Transport Processing/ Recovery Collection Disposal Recycling/ Reuse Figure 5.1 Functional Elements in a Solid-waste Treatment System. 62
  63. 63. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 5.3.3 Waste Minimization Waste minimization means the optimization process to minimize the waste come out of the plant. It will be done by source reduction and recovery of the sources. The source reduction refers to preventative measured taken to reduce the amount of waste, which produced in this process. Recovery of the sources is aimed to reuse the excess methanol to produce the MTBE. Waste production from the plant could be reduced by implementing these procedures: - Raw material modification, - Product reformulation, - Process modification, - Improvement in operating practices. The most important is by improving the product yield and this means minimization of waste generation. It will be accomplished through improvement in catalyst efficiency and proper maintenance activities. 63
  64. 64. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CHAPTER 6 SAFETY CONSIDERATION 6.1 INTRODUCTION For years, those employed in the chemical industry have known that the safe operation of chemical plant is essential to the industry’s continued ability to survive. The human, political and financial costs of having accidents are just too high for the chemical industry to not exhibit excellence in their efforts to operate plants in safe and environmentally responsible ways. The chemical industry has an outstanding record in both transportation safety and the safe operations of its processes. That effort has resulted in a dramatic and steady decline in releases and waste produced at chemical sites. Actions that should be taken to avoid serious chemical plant accidents are as follows: 1. In most cases involving large volumes of highly hazardous chemicals, excess flow valves are in place that would stop a rapid flow of the chemicals 2. When highly hazardous chemicals are involved, processes have fixed protection, as well as trained emergency response teams that could handle the incident. 3. Appropriate reaction control or inhibiting systems are in place to interrupt runaway reactions if cooling, heating and pressure relief are not considered adequate. 4. Control systems are designed to detect heat or pressure of a chemical reaction and to control that reaction. 5. Work more closely with local and state law enforcement groups. 64
  65. 65. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 6.2 MATERIAL SAFETY DATA SHEET 6.2.1 Isobutane (Instrument Grade) Product Number(S): 0001020533, 0001020534, 0001020535, 0001020536 Synonyms: Methylpropane; Iso Company Identification: Chevron Phillips Chemical Company Lp 10001 Six Pines Drive The Woodlands, Tx 77380 Product Information: Msds Requests: (800) 852-5530 Technical Information: (800) 852-5531 Colorless liquefied gas, odorless. - Flammable gas. May cause flash fire - Contents under pressure - Detection of leak via sense of smell may not be possible if odorant has degraded - Contact with liquefied gas can cause frostbite - Liquid can cause eye and skin injury - Reduces oxygen available for breathing Physical And Chemical Properties Appearance and odor: colorless liquefied gas, odorless. Ph: na Vapor pressure: 72 psia @ 37.8 ºc Vapor density (air=1): 2.1 Boiling point: -12°c (10.4°f) Solubility: negligible Percent volatile: 100 % volume Specific gravity: 0.564 @ 15.6 ºc Evaporation rate: >1 65
  66. 66. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Immediate Health Effects: Eye: Because the liquid product evaporates quickly, it can have a severe chilling effect on eyes and can cause local freezing of tissues (frostbite). Symptoms may include pain, tearing, reddening, swelling and impaired vision. Skin: Because the liquid product evaporates quickly, it can have a severe chilling effect on skin and can cause local freezing of tissues (frostbite). Symptoms may include pain, itching, discoloration, swelling, and blistering. Not expected to be harmful to internal organs if absorbed through the skin. Ingestion: Material is a gas and cannot usually be swallowed. Inhalation: This material can act as a simple asphyxiant by displacement of air. Symptoms of asphyxiation may include rapid breathing, in coordination, rapid fatigue, excessive salivation, disorientation, headache, nausea, and vomiting. Convulsions, loss of consciousness, coma, and/or death may occur if exposure to high concentrations continues. First Aid Measures Eye: Flush eyes with water immediately while holding the eyelids open. Remove contact lenses, if worn, after initial flushing, and continue flushing for at least 15 minutes. Get immediate medical attention. Skin: Skin contact with the liquid may result in frostbite and burns. Soak contact area in tepid water to alleviate the immediate effects and get medical attention. Ingestion: No specific first aid measures are required because this material is a gas and cannot usually be swallowed. Inhalation: For emergencies, wear a niosh approved air-supplying respirator. Move the exposed person to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get immediate medical attention. 6.2.2 N-Butane N-Butane synonym with I-Butane, Butane, and Normal Butane is a flammable gas. NButane is heavier than air and may travel considerable distance to an ignition source. 66
  67. 67. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR N-Butane is listed under the accident prevention provisions of section 112(r) of the Clean Air Act (CAA) with threshold quantity (TQ) of 10000 pounds. Physical and Chemical Properties Parameter value Physical state units : Gas o Vapor pressure at 70 F : 31 psia Vapor density at STP : 2.07 Evaporation point : not available Boiling point : 31.1 o Freezing point : -0.5 o pH : not available Solubility : insoluble Odor and appearance : a colourless and odourless gas Stability : stable Condition to avoid : high temperature F C Handling and storage Protect cylinders from physical damage. Store in cool, dry, well- ventilated area away from heavily trafficked areas and emergency exits. Do not allow the temperature where cylinders are stored to exceed 130oF. Cylinders should be stored upright and firmly secured to prevent falling or being knocked over. Full and empty cylinders should be segregated. Use a “first in first out” inventory systems to prevent full cylinders from being stored for excessive periods of time. Never carry a compressed gas cylinder or a container of a gas in cryogenic liquid form in an enclosed space such as a car trunk, van or station wagon. A leak cans re4sult in a fire, explosion, asphyxiation or a toxic exposure. 6.2.3 Methanol Methanol synonyms with Methyl alcohol and in chemical family alcohol with the formula CH3OH. Methanol is a clear, colourless, mobile, volatile, flammable liquid and it’s soluble in water, alcohol and ether. 67
  68. 68. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Physical and Chemical properties: Parameter value Physical state : liquid Boiling Point : 64.7oc Vapor Pressure (20oc) : 128 mb Vapor Density (air=1) : 1.11 Solubility in water ,%wt : full Specific Gravity : 0.792 g/cm3 Appearance and odor : liquid-colorless-odor specific Fire and Explosion Hazard data: Flash point : closed cup: 12oc Flammable limits, % vol : Lel: 6, Uel : 36.5 Extinguishing media : Foam – CO2 –halogenated agents Special fire fighting : Avoid contact with oxidizing materials Unusual fire and explosion : Moderate Reactivity Data: Stability : Medium Conditions to avoid : Oxidizing materials Incompatibility : Sulfo-chromic mixtures Special Precautions Precaution to be taken in handling and storing Methanol: store in iron or steel containers or tanks. Small quantities can be stored in reinforced glass containers. 6.2.4 MTBE Physical state, appearance MTBE is chemically stable; it does not polymerize, nor will decompose under normal conditions of temperature and pressure. Unlike most ether, MTBE does not tend to form peroxides (auto-oxidize). The physical state of MTBE is that MTBE is in the form of liquid at room temperature (25oC). It is a colourless liquid with the billing point at 68
  69. 69. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 55.2oC 131.4oF. The freezing point of MTBE is –108.6oC –163.5oC. The density of MTBE at 25oC is 735g/cm3. Physical dangers MTBE is non-reactive. It does not react with air, water, or common materials of construction. The reactivity of MTBE with oxidizing materials is probably low. However, without definitive information, it should be assumed that MTBE reacts with strong oxidizers, including peroxides. Chemical dangers MTBE is highly flammable and combustible when exposed to heat or flame or spark, and it is a moderate fire risk. Vapours may form explosive mixtures with air. It is unstable in acid solutions. Fire may produce irritating, corrosive or toxic gases. Runoff from fire control may contain MTBE and its combustion products. Occupational exposure limits (OELs) Routes of Exposure Inhalation risk Like other ethers, inhalation of high levels of MTBE by animals or humans results in the depression of the central nervous system. Symptoms observe red in rats exposed to 4000 or 8000 ppm in air included labored respiration, ataxia, decreased muscle tone, abnormal gait, impaired treadmill performance, and decreased grip strength. These symptoms were no longer evident 6 hours after exposure ceased. A lower level of MTBE, 800ppm did not produce apparent effects (Daughtrey et al., 1997). A number of investigations have been conducted to examine the self-reported acute MTBE in gasoline vapors during use by consumers. This research includes both epidemiological studies and studies involving controlled exposure of volunteers to MTBE at concentrations similar to those encountered in refueling an automobile (Reviewed in USEPA, 1997, and California EPA, 1998). In general, the studies involving controlled human exposures in chambers to levels of MTBE similar to those experienced during refueling and driving an automobile have not shown effects of 69
  70. 70. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR MTBE on physical symptoms (e.g. irritation), mood, or performance based tests of neurobehavioral function. 6.2.5 TBA (TERT - BUTYL ACOHOL) CAS Number: 75-65-0 Synonyms: tert-Butanol 2-methyl-2-propanol TBA t-butylhydroxide 1,1-dimethylethanol trimethylmethanol trimethylcarbinol Recognition NIOSH/OSHA Health Guideline. Summarizes pertinent information about for workers and employers as well as for physicians, industrial hygienists,and other occupational safety and health professionals who may need such information to conduct effective occupational safety and health programs. Evaluation 1. Health Hazards. Routes of exposure, summary of toxicology, signs and symptoms, emergency procedure. 2. Workplace Monitoring and Measurement. 3. Medical Surveillance. Workers who may be exposed to chemical hazards should be monitored in a systematic program of medical surveillance that is intended to prevent occupational injury and disease. The program should include education of employers and workers about work-related hazards, placement of workers in jobs that do not jeopardize their safety or health, early detection of adverse health effects, and referral of workers for diagnosis and treatment. 70
  71. 71. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Controls 1. Exposure Sources and Control Methods. 2. Personal Hygiene Procedures. 3. Respiratory Protection. Conditions for respirator use, respiratory protection program. 4. Personal Protective Equipment. Protective clothing should be worn to prevent any possibility of skin contact. Chemical protective clothing should be selected on the basis of available performance data, manufacturers' recommendations, and evaluation of the clothing under actual conditions of use. 5. Emergency Medical Procedures. Material Safety Data Sheets (MSDS's) include chemical specific information on emergency medical and first aid procedures as referenced under the OSHA Hazard Communication standard, 29 CFR 1910.1200, (g)(2)(X). This standard requires chemical manufacturers and importers to obtain or develop an MSDS for each hazardous chemical they produce or import. Employers shall have an MSDS in the workplace for each hazardous chemical, which they use. 6. Storage. 7. Spills and Leaks. In the event of a spill or leak, persons not wearing protective equipment and clothing should be restricted from contaminated areas until cleanup has been completed. 6.3 HAZARD IDENTIFICATION & EMERGENCY SAFETY & HEALTH RISK ASSESSMENT Safety & Health Risks vary with the type of industry & the magnitude of the emergency. The severity of the risk too will vary with especially where there are chemicals, combustible gases, potential for fire & explosion etc. These hazards may not only pose a danger to the health of working in a particular plant but also the adjacent community. In the event of a major disaster property both within and outside the plant will be damaged. The real and potential hazards at the work place must be identified and the Safety & Health Risks that they pose assessed. This will require a close scrutiny of all 71
  72. 72. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR work place buildings, their design, electrical wiring, transport and storage facilities, the work processes, workstation design, safe operating procedures, list of chemicals substances used, their quantity, storage, daily transfer, safe usage and disposal. MSDS’s of the chemical too have to be studied as regards their toxicity, volatility, and their potential for a fire and/or explosion and adverse health affects both short term and long term. The possible emergencies/disaster in a industry could be: • Fire/ explosion • Chemical spill • Radioactive material spill • Biological material spill • Personal injury The best action plan is prevention from an emergency. This is where one has to work closely with operation personnel to make sure that all operations are safe and comply with OSH Legislations. All persons at work are aware of the safe procedure and also follow those procedures. Unfortunately in the real world, mostly human factors- accident & emergency do occur. This is why emergency response plans have to be written up, communicated to all concerned and tested for effectiveness. Depending on the gravity the workplace emergency can be categorized in to Level 1, Level 2, or Lever 3 emergency. Level 1 Emergency- the first responder without having to call the disaster response team or outside help can effectively manage such incident. Examples; a small fire easily smothered, chemical spill easily contained and cleaned, injury minor and treated at site by rendering first aid. Level 2 Emergency - an incident that requires technical assistance from the disaster response team and may need outside help. Examples; fire that need technical from trained personnel and specialized equipment spill that can only be properly contained by specialized equipment. 72
  73. 73. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Level 3 Emergency- these are major disaster that are difficult to contain even with trained personnel and outside help. Examples, spill that cannot be properly contained or abated even by highly trained team and the use of sophisticated special equipment. Fire involving toxic material that is too large to control and are to burn. This may require the evacuation of civilians across jurisdictional boundaries 73
  74. 74. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR CHAPTER 7 MASS BALANCE 7.1 SNAMPROGETTI UNIT (REACTOR AND REGENERATOR) Stream S5 = 164.74 kgmole/hr 0.393 C4H8 0.393 H2 0.212 iC4H10 0.002 nC4H10 100 kgmole/hr 0.996 iC4H10 0.004 nC4H10 S2 Given from MSDS Assume steady-state system, Basis = 100 kgmole/hr of S2 74
  75. 75. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR The fraction at stream S2 acquired from isobutane instrument grade, MSDS. Reaction occurred in the reactor, iC4H10 C4H8 + H2 Flowrate in kgmole/hr of iC4H10 in the feed stream of S2 = 0.996 (100) = 99.6 kgmole/hr iC4H10 Balanced Based upon the stoichoimetric ratio with 65% conversion of iC4H10 to obtain C4H8. Since, 65% conversion in the reactor, ∴ kgmole/hr of C4H8 obtained = 0.65 (99.6) = 64.74 kgmole/hr ∴ 35% of iC4H10 unreacted = 99.6 - 64.74 = 34.86 kgmole/hr Based upon stoichiometric ratio (inert) (unreacted) n C4H10 + iC4H10 0.4 C4H8 99.6 H2 64.74 (kgmole/hr) + iC4H10 64.74 + n C4H10 34.86 0.4 (kgmole/hr) Input S2 Stream Component + (inert) MW Molar flow Output S5 Mass flow kg/hr Molar flow Mass flow kg/hr kg/kgmole kgmole/hr C4H8 56 - - kgmole/hr 64.74 3625.44 H2 2 - - 64.74 129.4 iC4H10 58 99.6 5776.8 34.86 2021.88 n C4H10 Total 58 0.4 23.2 5800 0.4 23.4 5800 75
  76. 76. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR 7.2 SEPARATOR Stream S10 = 64.74 kgmole/hr 1 H2 Stream S9 = 164.74 kgmole/hr 0.393 C4H8 0.393 H2 0.212 iC4H10 Stream S11 = 100 kgmole/hr 0.002 nC4H10 0.6474 C4H8 0.3486 iC4H10 0.0040 nC4H10 Input S9 Stream Component Output S10 S11 MW Molar flow Mass flow Molar flow Mass flow Molar flow Mass flow kg/kgmole kgmole/hr kg/hr kgmole/hr kg/hr kgmole/hr kg/hr C4H8 56 - - - - 64.74 3625.44 H2 2 - - 64.74 129.4 64.74 129.4 iC4H10 58 99.6 5776.8 - - 34.86 2021.88 n C4H10 Total 58 0.4 23.2 5800 - 129.4 0.4 23.4 5670.6 7.3 MIXER S13 = 64.74kgmole/hr S14 = 71.62 kgmole/hr 1 CH3OH 0.996 CH3OH 0.004 H2O S27 = 0.406 kgmole/hr 0.3596 CH3OH 0.6404 H2O 76
  77. 77. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR Input Stream Component S13 MW Molar flow Output S14 S27 Mass flow Molar flow Mass flow Molar flow Mass flow kg/kgmole kgmole/hr kg/hr kgmole/hr kg/hr kgmole/hr kg/hr CH3OH 32 71.214 2278.848 0.146 4.67 71.36 2283.52 H2O Total 18 - 2278.848 0.26 4.68 9.356 0.26 4.685 2288.205 7.4 MTBE REACTOR Assumption : 98% conversion of C4H8 (2% remains unconverted) Reactions involve in the reactor, 1. C4H8 + CH3OH 2. 2CH3OH 3. C4H8 + C5H12O C2H6O H2O + H2O C4H10O Stream S11 = 100 kgmole/hr 0.6474 C4H8 0.3486 iC4H10 0.0040 nC4H10 R e ac to r S15 kgmole/hr C4H8 iC4H10 nC4H10 S14 = 71. 214 kgmole/hr CH3OH CH3OH H2O C5H12O C4H10O C2H6O H2O 7.4.1 1st REACTION IN REACTOR C4H8 + CH3OH C5H12O 77
  78. 78. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR kgmole/hr of C4H8 in the stream S11 = 100(0.6474) = 64.74 kgmole/hr C4H8 Balance based upon stoichiometric ratio with 98% conversion. CH3OH is classified an excess. The unreacted of CH3OH (excess) = (71.36 - 64.74) = 6.62 kgmole/hr Since 98% conversion in the reactor, kgmole/hr of C5H12O obtained = 0.98 (64.74) = 63.44 kgmole/hr C5H12O obtained From the stoichiometric ratio, 98% C4H8 64.74 + CH3OH 71.214 C5H12O + C4H8 63.44 conv. + 1.3 CH3OH 7.92 unconverted kgmole/hr kgmole/hr 64.74 kgmole/hr 1 C4H8 R e ac to r kgmole/hr C4H8 CH3OH C5H12O 64.74 kgmole/hr 1 CH3OH Component MW Input Molar flow Mass flow Output Molar flow Mass flow 78
  79. 79. PRODUCTION OF 300,000 METRIC TON OF MTBE PER YEAR C4H8 (kg/kgmole) 56 (kgmole/hr) 64.74 (kg/hr) 3625.44 (kgmole/hr) 1.3 (kg/hr) 72.8 CH3OH 32 71.36 2283.52 7.92 253.44 C5H12O Total 88 - 5908.96 63.44 5582.72 5908.96 7.4.2 2nd REACTION IN REACTOR From 2nd reaction, stoichiometric ratio shown below: Since the ratio between methanol and dimethylether is 2CH3OH : 1C2H6O , 98% conversion methanol (CH3OH) into dimethylether (C2H6O) = 1.3 (0.98) 2 = 0.637 kgmole/hr 98% 2CH3OH conv. 7.92 C2H6O + 3.88 H2O + 2CH3OH 3.88 0.16 unconverted kgmole/hr 7.92 kgmole/hr 1 CH3OH kgmole/hr R e ac to r kgmole/hr CH3OH C2H6O H2O Input Output 79