<p>Preface xix</p> <p>Acknowledgments xxi</p> <p>About the Author xxiii</p> <p><b>1 Introduction 1</b></p> <p>References 6</p> <p><b>2 Composition of Crude Oils and Petroleum Products 7 </b></p> <p>2.1 Hydrocarbons 8</p> <p>2.1.1 Alkynes Series 12</p> <p>2.2 Aromatic Hydrocarbons 14</p> <p>2.3 Heteroatomic Organic Compounds 15</p> <p>2.3.1 Non-Hydrocarbons 15</p> <p>2.3.2 Sulfur Compounds 18</p> <p>2.4 Thiols 18</p> <p>2.5 Oxygen Compounds 20</p> <p>2.6 Nitrogen Compounds 22</p> <p>2.7 Resins and Asphaltenes 23</p> <p>2.8 Salts 24</p> <p>2.9 Carbon Dioxide 24</p> <p>2.10 Metallic Compounds 24</p> <p>2.11 Products Composition 25</p> <p>2.11.1 Liquefied Petroleum Gas (LPG) (C<sub>3</sub> and C<sub>4</sub>) 26</p> <p>2.11.2 Gasoline (C<sub>5</sub> to C<sub>11</sub>) 26</p> <p>2.11.3 Condensate (C<sub>4</sub>, C<sub>5</sub> and C<sub>6</sub> >) 27</p> <p>2.11.4 Gas Fuel Oils (C<sub>12</sub> to C<sub>19</sub>) 27</p> <p>2.11.5 Kerosene 27</p> <p>2.11.6 Diesel Fuel 28</p> <p>2.11.7 Fuel Oils # 4, 5, and 6 28</p> <p>2.11.8 Residual Fuel Oil 28</p> <p>2.11.9 Natural Gas 29</p> <p>References 30</p> <p><b>3 Characterization of Petroleum and Petroleum Fractions 31</b></p> <p>3.1 Introduction 31</p> <p>3.1.1 Crude Oil Properties 32</p> <p>3.1.2 Gravity, API 32</p> <p>3.1.3 Boiling Point Range 33</p> <p>3.1.4 Characterization Factor 33</p> <p>3.1.5 The Universal Oil Product Characterization factor, K<sub>UOP</sub> 34</p> <p>3.1.6 Carbon Residue, wt% 34</p> <p>3.1.7 Nitrogen Content, wt% 36</p> <p>3.1.8 Sulfur Content, wt% 36</p> <p>3.1.9 Total Acid Number (TAN) 36</p> <p>3.1.10 Salt Content, pounds/1000 barrels 36</p> <p>3.1.11 Metals, parts/million (ppm) by weight 36</p> <p>3.1.12 Pour Point (<sup>o</sup>F or <sup>°</sup>C) 36</p> <p>3.2 Crude Oil Assay Data 37</p> <p>3.2.1 Whole crude oil average properties 37</p> <p>3.2.2 Fractional properties 37</p> <p>3.3 Crude Cutting Analysis 37</p> <p>3.4 Crude Oil Blending 37</p> <p>3.5 Laboratory Testing of Crude Oils 46</p> <p>3.5.1 True Boiling Point (TBP) Curve 46</p> <p>3.5.2 ASTM D86 Distillation 46</p> <p>3.5.3 Boiling Points 47</p> <p>3.5.4 Conversion Between ASTM and TBP Distillation 49</p> <p>3.5.5 Petroleum Pseudo-Components 54</p> <p>3.5.6 Pseudo-Component Normal Boiling Points 55</p> <p>3.5.7 ASTM D1160 Distillation 55</p> <p>3.5.8 Determination of ASTM IBP, 10%, 20–90% Points of Blend 55</p> <p>3.5.9 ASTM 10–90% Points 56</p> <p>3.5.10 Initial Boiling Point Determination 56</p> <p>3.5.11 ASTM End Point of Blend 56</p> <p>3.5.12 Flash Point 56</p> <p>3.5.13 Flash Point, <sup>°</sup>F, as a Function of Average Boiling Point 57</p> <p>3.5.14 Smoke Point of Kerosenes 57</p> <p>3.5.15 Luminometer Number 57</p> <p>3.5.16 Reid Vapor Pressure (RVP) 57</p> <p>3.5.17 Vapor Pressure of Narrow Hydrocarbon Cuts 58</p> <p>3.6 Octanes 58</p> <p>3.7 Cetanes 58</p> <p>3.7.1 Cetane Index 59</p> <p>3.8 Diesel Index 59</p> <p>3.9 Determination of the Lower Heating Value of Petroleum Fractions 59</p> <p>3.10 Aniline Point Blending 60</p> <p>3.11 Correlation Index (CI) 60</p> <p>3.12 Chromatographically Simulated Distillations 61</p> References 62 <p><b>4 Thermodynamic Properties of Petroleum and Petroleum Fractions 63</b></p> <p>4.1 K-Factor Hydrocarbon Equilibrium Charts 64</p> <p>4.2 Non-Ideal Systems 72</p> <p>4.3 Vapor Pressure 74</p> <p>4.3.1 Vapor Pressure Determination using the Clausius-Clapeyron and the Antoine Equations 75</p> <p>4.4 Viscosity 80</p> <p>4.4.1 Conversion to Saybolt Universal Viscosity 80</p> <p>4.4.2 Conversion to Saybolt Furol Viscosity 82</p> <p>4.4.3 Equivalents of Kinematic (cSt), Saybolt Universal (SUS), and Dynamic viscosity 82</p> <p>4.4.4 Viscosity of Liquid Hydrocarbons 83</p> <p>4.4.5 Gas Viscosity 84</p> <p>4.5 Refractive Index 87</p> <p>4.6 Liquid Density 89</p> <p>4.6.1 Gas Density 89</p> <p>4.7 Molecular Weight 90</p> <p>4.8 Molecular Type Composition 90</p> <p>4.9 Critical Temperature, T<sub>c</sub> 96</p> <p>4.10 Critical Pressure, P<sub>c</sub> 97</p> <p>4.11 Pseudo-Critical Constants and Acentric Factors 98</p> <p>4.12 Enthalpy of Petroleum Fractions 99</p> <p>4.13 Compressibility Z Factor of Natural Gases 100</p> <p>4.14 Simulation Thermodynamic Software Programs 105</p> <p>References 110</p> <p><b>5 Process Descriptions of Refinery Processes 111</b></p> <p>5.1 Introduction 111</p> <p>5.2 Refinery and Distillation Processes 115</p> <p>5.3 Process Description of the Crude Distillation Unit 120</p> <p>5.3.1 Crude Oil Desalting 121</p> <p>5.3.2 Types of Salts in Crude Oil 122</p> <p>5.3.3 Desalting Process 122</p> <p>5.3.4 Pumparound Heat Removal 127</p> <p>5.3.5 Tower Pressure Drop and Flooding 130</p> <p>5.3.6 Carbon Steel Trays 130</p> <p>5.3.7 Rectifying Section of the Main Column 130</p> <p>5.3.8 Side Stripping Columns 130</p> <p>5.3.9 Crude Column Overhead 130</p> <p>5.3.10 General Properties of Petroleum Fractions 130</p> <p>5.4 Process Variables in the Design of Crude Distillation Column 132</p> <p>5.4.1 Process Design of a Crude Distillation Column 133</p> <p>5.5 Process Simulation 134</p> <p>5.5.1 Overall Check of Simulation 135</p> <p>5.5.2 Other Aspects of Design 136</p> <p>5.5.3 Relationship between Actual Trays and Theoretical Trays 137</p> <p>5.6 Process Description of Light Arabian Crude Using UniSim<sup>®</sup> Simulation Software [12] 138</p> <p>5.6.1 Column Conventions 141</p> <p>5.6.2 Performance Specifications Definition 142</p> <p>5.6.3 Cut Points 142</p> <p>5.6.4 Degree of Separation 142</p> <p>5.6.5 Overflash 142</p> <p>5.6.6 Column Pressure 143</p> <p>5.6.7 Overhead Temperature 143</p> <p>5.6.8 Bottom Stripping 144</p> <p>5.6.9 Side Stream Stripper 144</p> <p>5.6.10 Reflux 144</p> <p>5.7 Troubleshooting Actual Columns 144</p> <p>5.8 Health, Safety and Environment Considerations 145</p> <p>References 148</p> <p><b>6 Thermal Cracking Processes 149</b></p> <p>6.1 Process Description 152</p> <p>6.2 Steam Jet Ejector 152</p> <p>6.3 Pressure Survey in a Vacuum Column 154</p> <p>6.4 Simulation of Vacuum Distillation Unit 156</p> <p>6.5 Coking 157</p> <p>6.5.1 Delayed Coking 157</p> <p>6.5.2 Delayed Coker Yield Prediction 161</p> <p>6.5.3 Coke Formation 162</p> <p>6.5.4 Thermodynamics of Coking of Light Hydrocarbons 162</p> <p>6.5.5 Gas Composition 163</p> <p>6.6 Fluid Coking 164</p> <p>6.6.1 Flexi-Coking 165</p> <p>6.6.2 Contact Coking 167</p> <p>6.6.3 Coke Drums 168</p> <p>6.6.4 Heavy Coker Gas Oil (HCGO) Production 170</p> <p>6.6.5 Light Coker Gas Oil (LCGO) Production 170</p> <p>6.7 Fractionator Overhead System 170</p> <p>6.8 Coke Drum Operations 172</p> <p>6.9 Hydraulic Jet Decoking 173</p> <p>6.10 Uses of Petroleum Coke 174</p> <p>6.11 Use of Gasification 174</p> <p>6.12 Sponge Coke 175</p> <p>6.13 Safety and Environmental Considerations 175</p> <p>6.14 Simulation/Calculations 176</p> <p>6.15 Visbreaking 177</p> <p>6.15.1 Visbreaking Reactions 180</p> <p>6.15.2 Visbreaking Severity 180</p> <p>6.15.3 Operation and Control 180</p> <p>6.15.4 Typical Visbreaker Unit 181</p> <p>6.15.5 Typical Visbreaker Unit with Vacuum Flasher 182</p> <p>6.15.6 Typical Combination Visbreaker and Thermal Cracker 183</p> <p>6.15.7 Product Yield 183</p> <p>6.16 Process Simulation 184</p> <p>6.17 Health, Safety and Environment Considerations 185</p> References 186 <p><b>7 Hydroprocessing 187</b></p> <p>7.1 Catalytic Conversion Processes 187</p> <p>7.1.1 Hydrocracking Chemistry 188</p> <p>7.1.2 Hydrocracking Reactions 190</p> <p>7.1.3 Typical Hydrocracking Reactions 191</p> <p>7.2 Feed Specifications 194</p> <p>7.2.1 Space Velocity 195</p> <p>7.2.2 Reactor Temperature 195</p> <p>7.2.3 Reactor Pressure 195</p> <p>7.2.4 Hydrogen Recycle Rate 195</p> <p>7.2.5 Oil Recycle Ratio 195</p> <p>7.2.6 Heavy Polynuclear Aromatics 196</p> <p>7.3 Feed Boiling Range 196</p> <p>7.4 Catalyst 196</p> <p>7.4.1 Catalyst Performance 197</p> <p>7.4.2 Loss of Catalyst Performance 197</p> <p>7.4.3 Poisoning by Impurities in Feeds or Catalysts 198</p> <p>7.4.4 The Apparent Catalyst Activity 200</p> <p>7.5 Poor Gas Distribution 200</p> <p>7.6 Poor Mixing of Reactants 200</p> <p>7.7 The Mechanism of Hydrocracking 200</p> <p>7.8 Thermodynamics and Kinetics of Hydrocracking 201</p> <p>7.9 Process Design, Rating and Performance 204</p> <p>7.9.1 Operating Temperature and Pressure 205</p> <p>7.9.2 Optimum Catalyst Size and Shape 205</p> <p>7.9.3 Pressure Drop (ΔP) in Tubular/Fixed-Bed Reactors 205</p> <p>7.9.4 Catalyst Particle Size 207</p> <p>7.9.5 Vessel Dimensions 208</p> <p>7.10 Increased ΔP 210</p> <p>7.11 Factors Affecting Reaction Rate 214</p> <p>7.12 Measurement of Performance 215</p> <p>7.13 Catalyst-Bed Temperature Profiles 216</p> <p>7.14 Factors Affecting Hydrocracking Process Operation 217</p> <p>7.15 Hydrocracking Correlations 217</p> <p>7.15.1 Maximum Aviation Turbine Kerosene (ATK) Correlations 219</p> <p>7.15.2 Process Description 220</p> <p>7.15.3 Fresh Feed and Recycle Liquid System 224</p> <p>7.15.4 Liquid and Vapor Separators 225</p> <p>7.15.5 Recycle Gas Compression and Distribution 226</p> <p>7.15.6 Hydrogen Distribution 226</p> <p>7.15.7 Control of the Hydrogen System 226</p> <p>7.15.8 Reactor Design 227</p> <p>7.16 Hydrocracker Fractionating Unit 228</p> <p>7.16.1 Mild Vacuum Column 230</p> <p>7.16.2 Steam Generation 230</p> <p>7.17 Operating Variables 231</p> <p>7.18 Hydrotreating Process 234</p> <p>7.18.1 Process Description 237</p> <p>7.18.2 Process Variables 237</p> <p>7.18.3 Hydrotreating Catalysts 240</p> <p>7.19 Thermodynamics of Hydrotreating 240</p> <p>7.20 Reaction Kinetics 243</p> <p>7.21 Naphtha Hydrotreating 245</p> <p>7.21.1 Hydrotreating Correlations 245</p> <p>7.21.2 Middle Distillates Hydrotreating 248</p> <p>7.21.3 Middle Distillate Hydrotreating Correlations 248</p> <p>7.22 Atmospheric Residue Desulfurization 250</p> <p>7.22.1 High-Pressure Separator 252</p> <p>7.22.2 Low-Pressure Separator 252</p> <p>7.22.3 Hydrogen Sulfide Removal 252</p> <p>7.22.4 Recycled Gas Compressor 252</p> <p>7.22.5 Process Water 252</p> <p>7.22.6 Fractionation Column 253</p> <p>7.22.7 Operating Conditions of Hydrotreating Processes 253</p> <p>7.23 Health, Safety and Environment Considerations 258</p> <p>References 258</p> <p><b>8 Catalytic Cracking 259 </b></p> <p>8.1 Introduction 259</p> <p>8.2 Fluidized Bed Catalytic Cracking 262</p> <p>8.2.1 Process Description 262</p> <p>8.3 Modes of Fluidization 269</p> <p>8.4 Cracking Reactions 270</p> <p>8.4.1 Secondary Reactions 272</p> <p>8.5 Thermodynamics of FCC 273</p> <p>8.5.1 Transport Phenomena, Reaction Patterns and Kinetic models 273</p> <p>8.5.2 Three- and Four-Lump kinetic models 276</p> <p>8.6 Process Design Variables 278</p> <p>8.6.1 Process Variables 279</p> <p>8.6.2 Process Operational Variables 280</p> <p>8.7 Material and Energy Balances 281</p> <p>8.7.1 Material Balance 281</p> <p>8.7.2 Energy Balance 282</p> <p>8.8 Heat Recovery 283</p> <p>8.9 FCC Yield Correlations 284</p> <p>8.10 Estimating Potential Yields of FCC Feed 286</p> <p>8.11 Pollution Control 290</p> <p>8.12 New Technology 292</p> <p>8.12.1 Deep Catalytic Cracking 293</p> <p>8.12.2 Shell’s Fluid Catalytic Cracking 294</p> <p>8.12.3 Fluid Catalytic Cracking High Severity 295</p> <p>8.12.4 Fluid Catalytic Cracking for Maximum Olefins 295</p> <p>8.13 Refining/Petrochemical Integration 296</p> <p>8.14 Metallurgy 296</p> <p>8.15 Troubleshooting for Fluidized Catalyst Cracking Units 297</p> <p>8.16 Health, Safety and Environment Considerations 298</p> <p>8.17 Licensors’ Correlations 299</p> <p>8.18 Simulation and Modeling Strategy 300</p> References 304<br /> <p><b>9 Catalytic Reforming and Isomerization 305</b></p> <p>9.1 Introduction 305</p> <p>9.2 Catalytic Reforming 306</p> <p>9.3 Feed Characterization 306</p> <p>9.4 Catalytic Reforming Processes 308</p> <p>9.4.1 Role of Reformer in the Refinery 309</p> <p>9.4.2 UOP Continuous Catalytic Regeneration (CCR) Reforming Process 310</p> <p>9.5 Operations of the Reformer Process 312</p> <p>9.5.1 Effect of Major Variables in Catalytic Reforming 314</p> <p>9.6 Catalytic Reformer Reactors 316</p> <p>9.7 Material Balance in Reforming 317</p> <p>9.8 Reactions 320</p> <p>9.8.1 Naphthene Dehydrogenation to Cyclohexanes 320</p> <p>9.8.2 Dehydrocyclization of Paraffins to Aromatics 321</p> <p>9.8.3 Dehydroisomerization of Alkylcyclopentanes to Aromatics 321</p> <p>9.8.4 Isomerization of n-Paraffins 321</p> <p>9.9 Hydrocracking Reactions 322</p> <p>9.10 Reforming Catalyst 322</p> <p>9.11 Coke Deposition 324</p> <p>9.12 Thermodynamics 326</p> <p>9.13 Kinetic Models 326</p> <p>9.14 The Reactor Model 326</p> <p>9.15 Modeling of Naphtha Catalytic Reforming Process 329</p> <p>9.16 Isomerization 329</p> <p>9.16.1 Thermodynamics 330</p> <p>9.16.2 Isomerization Reactions 331</p> <p>9.17 Sulfolane Extraction Process 331</p> <p>9.17.1 Sulfolane Extraction Unit (SEU) Corrosion Problems 332</p> <p>9.17.2 Other Solvents for the Extraction Unit 333</p> <p>9.18 Aromatic Complex 333</p> <p>9.18.1 Aromatic Separation 335</p> <p>9.19 Hydrodealkylation Process 336</p> <p>9.19.1 Separation of the Reactor Effluents 337</p> References 337 <p><b>10 Alkylation and Polymerization Processes 339 </b></p> <p>10.1 Introduction 339</p> <p>10.2 Chemistry of Alkylation 340</p> <p>10.3 Catalysts 342</p> <p>10.4 Process Variables 343</p> <p>10.5 Alkylation Feedstocks 345</p> <p>10.6 Alkylation Products 346</p> <p>10.7 Sulfuric Acid Alkylation Process 346</p> <p>10.8 HF Alkylation 347</p> <p>10.9 Kinetics and Thermodynamics of Alkylation 351</p> <p>10.10 Polymerization 354</p> <p>10.11 HF and H<sub>2</sub>SO<sub>4</sub> Mitigating Releases 354</p> <p>10.12 Corrosion Problems 356</p> <p>10.13 A New Technology of Alkylation Process Using Ionic Liquid 356</p> <p>10.14 Chevron – Honeywell UOP Ionic liquid Alkylation 357</p> <p>10.15 Chemical Release and Flash Fire: A Case Study of the Alkylation Unit at the Delaware City Refining Company (DCRC) Involving Equipment Maintenance Incident 358</p> <p>References 362</p> <p><b>11 Hydrogen Production and Purification 365 </b></p> <p>11.1 Hydrogen Requirements in a Refinery 365</p> <p>11.2 Process Chemistry 366</p> <p>11.3 High-Temperature Shift Conversion 368</p> <p>11.4 Low-Temperature Shift Conversion 368</p> <p>11.5 Gas Purification 368</p> <p>11.6 Purification of Hydrogen Product 369</p> <p>11.7 Hydrogen Distribution System 370</p> <p>11.8 Off-Gas Hydrogen Recovery 371</p> <p>11.9 Pressure Swing Adsorption (PSA) Unit 371</p> <p>11.10 Refinery Hydrogen Management 375</p> <p>11.11 Hydrogen Pinch Studies 377</p> <p>References 379</p> <p><b>12 Gas Processing and Acid Gas Removal 381 </b></p> <p>12.1 Introduction 381</p> <p>12.2 Diesel Hydrodesulfurization (DHDS) 383</p> <p>12.3 Hydrotreating Reactions 383</p> <p>12.4 Gas Processing 388</p> <p>12.4.1 Natural Gas 388</p> <p>12.4.2 Gas Processing Methods 389</p> <p>12.4.3 Reaction Gas Processes 390</p> <p>12.4.4 Sweetening Process 390</p> <p>12.4.5 MEROX Process 390</p> <p>12.5 Sulfur Management 391</p> <p>12.5.1 Sulfur Recovery Processes 393</p> <p>12.5.2 Tail Gas Clean Up 401</p> <p>12.6 Physical Solvent Gas Processes 401</p> <p>12.6.1 Physical and Chemical Processes 402</p> <p>12.6.2 Advantages and Disadvantages of the Sulfinol<sup>®</sup> Process 402</p> <p>12.7 Carbonate Process 402</p> <p>12.8 Solution Batch Process 403</p> <p>12.9 Process Description of Gas Processing using UniSim<sup>®</sup> Simulation 405</p> <p>12.10 Gas Dryer (Dehydration) Design 410</p> <p>12.10.1 The Equations 412</p> <p>12.10.2 Pressure Drop (ΔP) 413</p> <p>12.10.3 Fouled Bed 413</p> <p>12.11 Kremser-Brown-Sherwood Method-No Heat of Absorption 415</p> <p>12.11.1 Absorption: Determine Component Absorption in Fixed Tray Tower (Adapted in part from Ref. 12) 415</p> <p>12.11.2 Absorption: Determine the Number of Trays for Specified Product Absorption 417</p> <p>12.11.3 Stripping: Determine the Number of Theoretical Trays and Stripping Steam or Gas Rate for a Component Recovery 418</p> <p>12.11.4 Stripping: Determine Stripping-Medium Rate for a Fixed Recovery 420</p> <p>12.12 Absorption: Edmister Method 421</p> <p>12.12.1 Absorption and Stripping Efficiency 427</p> <p>12.13 Gas Treating Troubleshooting 432</p> <p>12.13.1 High Exit Gas Dew Point 432</p> <p>12.13.2 High Glycol Losses 432</p> <p>12.13.3 Glycol Contamination 432</p> <p>12.13.4 Poor Glycol Reconcentration 433</p> <p>12.13.5 Low Glycol Circulation – Glycol Pump 433</p> <p>12.13.6 High Pressure Drop Across Contactor 433</p> <p>12.13.7 High Stripping Still Temperature 433</p> <p>12.13.8 High Reboiler Pressure 433</p> <p>12.13.9 Firetube Fouling/Hot Spots/Burn Out 433</p> <p>12.13.10 High Gas Dew Points 433</p> <p>12.13.11 Cause – Inadequate Glycol Circulation Rate 433</p> <p>12.13.12 Low Reboiler Temperature 433</p> <p>12.13.13 Flash Separator Failure 434</p> <p>12.13.14 Cause – Insufficient Reconcentration of Glycol 434</p> <p>12.13.15 Cause – Operating Conditions Different from Design 434</p> <p>12.13.16 Cause – Low Gas Flow Rates 434</p> <p>12.13.17 High Glycol Loss 434</p> <p>12.14 Cause – Loss of Glycol Out of Still Column 434</p> <p>12.15 The ADIP Process 435</p> <p>12.16 Sour Water Stripping Process 435</p> References 438<br /> <p>Glossary of Petroleum and Technical Terminology 441</p> <p>Appendix A Equilibrium K values 533</p> <p>Appendix B Analytical Techniques 547</p> <p>Appendix C Physical and Chemical Characteristics of Major Hydrocarbons 557</p> <p>Appendix D A List of Engineering Process Flow Diagrams and Process Data Sheets 573</p> <p>Index 623</p>