Fundamentals of Petroleum and Petrochemical Engineering Uttam Ray Chaudhuri University of Calcutta Calcutta, India CRC Press Taylor & Francis Group Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Croup, an Informa business
Preface Author Introduction xxiii xxv Chapter 1 Crude Petroleum Oil 1 1.1 Composition of Crude Oil 1 1.1.1 Hydrocarbon Groups 1 1.1.1.1 Complex Hydrocarbons 3 1.1.1.2 Non-Hydrocarbons or Hetero-Atomic Compounds 4 1.2 Physical Properties of Crude Oil 6 1.3 Origin of Hydrocarbons 7 1.4 Exploration Techniques 9 1.4.1 Gravimetric Method 9 1.4.2 Magnetometric Method 10 1.4.3 Seismic Survey 10 1.4.4 Remote Sensing Method 10 1.4.5 Geochemical Methods 11 1.4.6 Stratigraphy 11 1.5 Resource Estimation 11 1.5.1 Effect of Pressure 12 1.5.2 Connate Water 13 1.5.3 Effect of Temperature 13 1.5.4 Effect of Viscosity 13 1.6 Oil Field Development 14 1.7 Well Logging 16 1.8 Oil Production Processes 16 1.9 Crude Conditioning and Storage 19 1.10 Transportation and Metering of Crude Oil 20 1.11 Gas Hydrates 21 1.11.1 Production Method 22 1.12 Coal Bed Methane 22 23 Questions Chapter 2 Petroleum Products and Test Methods 25 2.1 Crude Oil Analysis 25 2.1.1 API Gravity 27 2.1.2 Characterisation Factor 27 2.1.3 Bottom Sediment and Water 28 xi
xii 2.2 Domestic Fuels 28 2.2.1 Liquified Petroleum Gas 28 2.2.2 Kerosene 30 2.2.2.1 Smoke Point 30 2.2.2.2 FlashPoint 31 2.2.2.3 Char Point and Bloom 31 2.2.2.4 Distillation Test 32 2.2.2.5 Sulfur Content and Corrosion 32 2.3 Automotive Fuels 32 2.3.1 Motor Spirit 32 2.3.1.1 American Standard for Testing Material Distillation 33 2.3.1.2 Octane Number 34 2.3.1.3 Corrosion 35 2.3.1.4 Reid Vapour Pressure 36 2.3.1.5 Oxidation Stability 36 2.3.1.6 Additives 36 2.3.2 High Speed Diesel 36 2.3.2.1 Cetane Number 37 2.3.2.2 Diesel Index 37 2.3.2.3 Sulfur 38 2.3.2.4 Corrosion 38 2.3.2.5 FlashPoint 38 2.3.2.6 Flame Length 38 2.3.2.7 Pour Point 38 2.3.2.8 Viscosity 38 2.4 Aviation Fuels 39 2.5 Furnace Fuels 39 2.5.1 Gaseous Fuels 39 2.5.2 Liquid Fuels 40 2.6 Lubricating Oils 40 2.6.1 Viscosity 41 2.6.2 Saybolt Method 41 2.6.3 Redwood Method 41 2.6.4 Brookfield Method 42 2.6.5 Viscosity Index 42 2.6.6 Cloud Point 43 2.6.7 Pour Point 43 2.7 Miscellaneous Products 44 2.7.1 Jute Batching Oil 44 2.7.2 Mineral Turpentine Oil 44 2.7.3 Carbon Black Feed Stock 46 2.7.4 Bitumen 46 2.7.5 Petroleum Coke 47 2.7.6 Wax 48 Questions 48
xiii Chapter 3 Processing Operations in a Petroleum Refinery 49 3.1 Crude Oil Receiving 49 3.2 Desalting of Crude Oil 49 3.3 Distillation and Stripping 51 3.3.1 Atmospheric Distillation 52 3.4 Stabilisation 54 3.5 Amine Absorption 55 3.6 De-Ethaniser 55 3.7 Meroxing and Caustic Wash 56 3.8 Liquified Petroleum Gas Splitter 58 3.9 Naphtha Redistillation 58 3.10 Naphtha Pretreatment 59 3.11 Naphtha Platinum Reforming (Platforming) 60 3.12 Kerosene Hydrodesulfurisation 62 3.13 Diesel Hydrodesulfurisation 63 3.14 Vacuum Distillation 64 3.15 Solvent Extraction 66 3.16 Propane Deasphalting 67 3.17 Solvent Dewaxing 67 3.18 Hydrofinishing 69 3.19 Catalytic Processes for Lube Oil Base Stock Manufacture... 70 3.20 Hydrocracking 71 3.21 Mild Hydrocracking 73 3.22 Hydrogen Generation 74 3.22.1 Feed Desulfurisation 74 3.22.2 Primary Reforming 74 3.22.3 Secondary Reforming 75 3.22.4 Shift Reactors 75 3.22.5 Hydrogen Purification 76 3.23 Fluid Catalytic Cracking 76 3.24 Bitumen Blowing 79 3.25 Vis-Breaking 79 3.26 Coking 80 Questions Si Chapter 4 Lubricating Oil and Grease 83 4.1 Components of Finished Lubricating Oils 83 4.2 Automotive Oils 84 4.3 Industrial Lubricants 85 4.3.1 Bearing Lubricants 85 4.3.2 Hydraulic Lubricants 86 4.3.3 Compressor Lubricants 86 4.3.4 Pump Lubricants 86 4.4 Aviation Lubricants 87
xiv 4.5 Marine Lubricants 88 4.6 Greases 88 4.7 Lube Blending and Grease Manufacture 89 4.8 Environmental Impact of Lubricants 90 4.9 Reclamation of Used Lubricants 92 4.10 Power Consumption in a Blending Tank 94 Questions 98 Chapter 5 Petrochemicals 101 5.1 Defintions of Petrochemicals 101 5.1.1 Feedstocks 101 5.1.2 Intermediates 101 5.1.3 Finished Products 102 5.2 Naphtha Cracking 103 5.2.1 Primary Fractionator or Stabiliser 105 5.2.2 Hydrogen Separator 105 5.3 Conversion Processes for Selected Petrochemicals 107 5.3.1 Polyethylene 107 5.3.1.1 Low Density Polyethylene 108 5.3.1.2 High Density Polyethylene 109 5.3.1.3 Linear Low Density Polyethylene 110 5.3.2 Polypropylene Ill 5.3.3 Polyethylene Terephthalate Ill 5.3.3.1 Terephthalic Acid 112 5.3.3.2 Ethylene Glycol 113 5.3.4 Polyvinyl Chloride 115 5.3.5 Polystyrene 115 5.3.6 Polybutadiene 116 5.3.7 Acrylonitrile Butadiene Styrene 116 5.3.8 Styrene-Butadiene Rubber 116 5.3.9 Poly Methyl Metha Acrylate 117 5.3.10 Polytetrafluoroethylene 117 5.3.11 Nylons 117 5.3.12 Phenol Formaldehyde 120 5.3.13 Urea Formaldehyde 120 5.3.14 Melamine Formaldehyde 120 5.3.15 Polyurethane 121 5.3.15.1 Toluene Diisocyanate 121 5.3.16 Silicone 122 5.4 Petrochemical Complex 122 5.4.1 Downstream Units 122 5.4.2 Petrochemicals' Hub 122 5.5 Processing of Plastic, Rubber, and Fibre 123 5.5.1 Moulding of Plastics 124 5.5.2 Extrusion Moulding 124
' xv 5.5.3 Blow Moulding 126 5.5.4 Compression Moulding 126 5.5.5 Thermal Moulding 126 5.5.6 Injection Moulding 126 5.5.7 Rubber Compounding 127 Questions 128 Chapter 6 Offsite Facilities, Power and Utilities 131 6.1 Layout of Petroleum and Petrochemical Plants 131 6.2 Processing Units 131 6.3 Offsite Facilities 134 6.3.1 Floating Roof Tank 134 6.3.2 Fixed Roof Tank 135 6.3.3 Pressure Vessels 136 6.3.4 Horton Sphere 136 6.3.5 Accessories 136 6.3.6 Blending Operations 139 6.3.7 Filling, Loading, and Despatch Operations 139 6.3.8 Pipeline Transport 139 6.3.9 Effluent Water Treatment 140 6.3.10 Off Gas Treatment 141 6.3.11 Internal Fuel Oil Circulation 144 6.4 Power and Steam Generating Plant 144 6.5 Cooling Tower 147 6.6 Water Conditioning Plant 147 Questions 150 Chapter 7 Material and Energy Balances 151 7.1 Measurement of Quantity of Crude Oil and Products 151 7.1.1 Tank Dipping 151 7.1.2 Volume Correction 153 7.1.3 Density Correction 153 7.2 Measurement of Gases in Closed Vessels 158 7.3 Material Balance in a Plant 158 7.3.1 Flow Meter Readings 160 7.3.2 Fuel Consumption 161 7.3.3 Steam Consumption 161 7.3.4 Overall Material Balance 161 7.4 Energy Balance in a Plant 164 7.4.1 Heat Balance 164 7.4.2 Energy Balance in a Heat Exchanger 164 Questions 7.4.3 Energy Balance in a Furnace 165 7.4.4 Energy Balance in a Distillation Column 166 7.4.5 Overall Energy Balance 168 170
xvi Chapter 8 Heat Exchangers and Pipe-Still Furnaces 171 8.1 Heat Exchangers 171 8.2 Theory of Heat Exchange 171 8.2.1 Heat Balance 173 8.2.2 Rate of Heat Transfer 174 8.3 Fouling 177 8.4 Plate Type Heat Exchanger 185 8.5 Extended Surface Exchanger 185 8.6 Scraped Surface Exchanger 185 8.7 Heat Exchanger Train 186 8.8 Pipe-Still Furnace 188 8.9 Pipe-Still Furnace Elements 190 8.9.1 Heater Pipes or Tubes 190 8.9.2 Refractories 191 8.9.3 Burners 191 8.9.4 Convection Zone 192 8.9.5 Radiant Section 192 8.9.6 Stack or Chimney 193 8.10 Operation of a Furnace 193 8.11 Draught in a Furnace 194 8.12 Furnace Design by the Wilson, Lobo and Hottel Method... 194 8.12.1 Furnace Design by the Lobo and Evans Method 205 Questions 206 Chapter 9 Distillation and Stripping 207 9.1 Processes of Distillation and Stripping 207 9.2 Batch Distillation 207 9.3 Boiling Point and Equilibrium Diagrams 208 9.4 Theory of Distillation 208 9.5 Continuous Distillation 210 9.5.1 Top Reflux Drum 211 9.5.2 Rectification Section 212 9.5.2.1 Streams Leaving the Envelope under Study 212 9.5.2.2 Streams Entering the Envelope under Study 212 9.5.2.3 Reboiler 213 9.5.2.4 Stripping Section 213 9.5.2.5 Feed Plate or Flash Zone 214 9.5.2.6 Evaluation of Fraction Vaporised (f) from the Quality of the Feed 215 9.6 McCabe-Thiele Method 217 9.6.1 Operating Line for the Feed Section or Feed Line..218 9.6.2 Operating Line and Plates for the Stripping Section 218
xvii 9.7 Enthalpy Balance Method 219 9.7.1 Reflux Drum 219 9.7.2 Top Plate 220 9.7.3 Reboiler 221 9.7.4 Numerical Solution 223 9.7.5 Types of Refluxes 229 9.7.6 Internal Reflux 230 9.7.7 Minimum Reflux 230 9.8 Gap and Overlap 230 9.9 Packie's Correlation 231 Question 234 Chapter 10 Extraction 235 10.1 Extraction Principle 235 10.2 Extraction Process 236 10.3 Definition of Terms Related to Extraction 236 10.3.1 Partition Coefficient 236 10.3.2 Partial Solubility 237 10.3.3 Solvent to Feed Ratio 237 10.3.4 Solvent Recovery 237 10.3.5 Separation of Phases 237 10.3.6 Selectivity 237 10.3.7 Solvent Power 238 10.3.8 Critical Solution Temperature 238 10.4 Phase Equilibrium in the Extraction Process 238 10.5 Batch Extraction 239 10.6 Continuous Extraction 240 10.6.1 Computation of Number of Plates 240 Questions 248 Chapter 11 Reactor Calculations 249 11.1 Reactors in Refineries and Petrochemical Plants 249 11.2 Reaction Stoichiometry, Mechanism, and Pathways 249 11.3 Rate of Reaction and Kinetic Equations 250 11.4 Batch, Continuous Stirred Tank Reactor, and Plug Flow Reactor Concepts 252 11.5 Naphtha Reformer Calculations 269 11.6 Calculations for a Fluidised Catalytic Cracking Reactor 271 Chapter 12 Elements of Pipeline Transfer Facilities 275 12.1 Pipes and Tubes 275 12.2 Fittings and Supports 275 12.2.1 Corrosion Protection 276
<v;jj 12.3 Crude Oil Transfer Lines 277 12.3.1 Design Steps for Crude Pipes 277 12.3.2 Economic Pipe Diameter 279 12.4 Product Transfer Lines 279 12.5 Gas Transfer Lines 280 12.6 Pumps and Compressors 281 12.6.1 Centrifugal Pumps 281 12.6.1.1 Priming 283 12.6.1.2 Specific Speed 285 12.6.2 Positive Displacement Pumps 287 12.6.3 Rotary Pumps 288 12.6.4 Compressors 289 12.7 Power Calculations for Pumping and Compression 290 Chapter 13 Instrumentation and Control in a Refinery 297 13.1 Control Hardware 297 13.1.1 Hardware 297 13.1.2 Cables 298 13.2 Control Loops 299 13.3 The Process Piping and Instrumentation Diagram 301 13.4 Control Software 301 13.5 Distributed Control System 304 13.6 The Control Room 305 13.7 Crude Throughput Control 305 13.8 Desalter Control 306 13.9 Atmospheric Distillation Column Control 308 13.9.1 Reflux Drum Pressure Control 308 13.9.2 Reflux Drum Level Control 308 13.9.3 Top Plate Temperature 310 13.9.4 Draw Plate Temperature 310 13.9.5 Overfiash Rate 312 13.9.6 Flash Zone Pressure and Temperature 312 13.9.7 Bottom Temperature 312 13.9.8 Furnace Control 312 13.10 Vacuum Distillation Control 312 13.11 Reformer Unit Control 314 13.12 Fluid Catalytic Cracking Unit Control 314 13.12.1 Reactor Outlet Temperature Control 316 13.12.2 Level Control of the Catalyst Bed in the Stripper Section of the Reactor 319 13.12.3 Pressure Balance between the Reactor and the Regenerator 319 13.13 Fail-Safe Devices 319 13.13.1 Normal Running Conditions 319 13.13.2 During Planned Shutdown 321
x'x 13.13.3 During Accidents or Emergency Shutdown 322 13.13.4 Power Plant Failure 323 13.14 Standard Signals in Process Control 323 Chapter 14 Miscellaneous 325 14.1 Startup 325 14.1.1 Power Plant Startup 325 14.1.2 Startup of a Crude Distillation Unit 326 14.1.3 Starting a Naphtha Pretreatment Plant 327 14.1.4 Starting a Naphtha Reforming Plant 328 14.1.5 Starting a Fluid Catalytic Cracking Plant 328 14.2 Shutdown 329 14.2.1 Shutdown of a Crude Distillation Unit 330 14.2.2 Shutdown of a Naphtha Pretreatment Unit 330 14.2.3 Regeneration of the Catalyst 330 14.2.4 Shutdown of a Naphtha Reforming Unit 331 14.2.5 Regeneration of Reforming Catalyst 331 14.3 Maintenance of Plant and Equipments 332 14.4 Fire and Explosion 333 14.4.1 Pyrophoric Iron 334 14.5 Factories Act 335 14.6 Safety Analysis 337 Chapter 15 Plant Management and Economics 343 15.1 Cost of Equipment 343 15.1.1 Capacity Ratio Method 343 15.1.2 Purchased Price 344 15.1.3 First Cost of the Equipment 344 15.1.4 Depreciation 344 15.2 Cost of a Plant 344 15.3 Operating Cost 344 15.4 Product Cost 344 15.5 Profit and Product Price 345 15.6 Taxes and Duties 345 15.7 Breakeven Point, Payout Period, and Rate of Return 345 15.7.1 Payout Period or Payback Period 346 15.7.2 Rate of Return 346 15.8 Linear Programming 349 15.9 Material Audit 352 15.9.1 Category of Materials 352 15.9.2 Papers to Be Maintained 353 15.9.2.1 Tank Dip Register 353 15.9.2.2 Pass Out Vouchers 353 15.9.2.3 Tank Dip Memos 353
XX 15.9.2.4 Daily Stock Report 355 15.9.2.5 Daily Pumping Record 355 15.9.2.6 Daily Operation Record 355 15.9.3 Material Audit of Capital Goods 366 15.10 Energy Audit 367 15.10.1 Electricity Audit 367 15.10.2 Thermal Audit 368 15.10.3 Steam Balance 368 Appendix Index 375 381