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FIFTH EDI T ION T h e C h e m i s t r y a n d T e c h n o l o g y o f P e t r o l e u m CHEMICAL INDUSTRIES A Series of Reference Books and Textbooks Founding Editor HEINZ HEINEMANN Berkeley, California Series Editor JAMES G. SPEIGHT CD & W, Inc. Laramie, Wyoming MOST RECENTLy PUbLISHED The Chemistry and Technology of Petroleum, Fifth Edition, James G. Speight Refining Used Lubricating Oils, James Speight and Douglas I. Exall Educating Scientists and Engineers for Academic and Non-Academic Career Success, James Speight Transport Phenomena Fundamentals, Third Edition, Joel Plawsky Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, Second Edition, Leslie R. Rudnick Modeling of Processes and Reactors for Upgrading of Heavy Petroleum, Jorge Ancheyta Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, Second Edition, Leslie R. Rudnick Fundamentals of Automatic Process Control, Uttam Ray Chaudhuri and Utpal Ray Chaudhuri The Chemistry and Technology of Coal, Third Edition, James G. Speight Practical Handbook on Biodiesel Production and Properties, Mushtaq Ahmad, Mir Ajab Khan, Muhammad Zafar, and Shazia Sultana Introduction to Process Control, Second Edition, Jose A. Romagnoli and Ahmet Palazoglu Fundamentals of Petroleum and Petrochemical Engineering, Uttam Ray Chaudhuri Advances in Fluid Catalytic Cracking: Testing, Characterization, and Environmental Regulations, edited by Mario L. Occelli Advances in Fischer-Tropsch Synthesis, Catalysts, and Catalysis, edited by Burton H. Davis and Mario L. Occelli Transport Phenomena Fundamentals, Second Edition, Joel Plawsky Asphaltenes: Chemical Transformation during Hydroprocessing of Heavy Oils, Jorge Ancheyta, Fernando Trejo, and Mohan Singh Rana Chemical Reaction Engineering and Reactor Technology, Tapio O. Salmi, Jyri-Pekka Mikkola, and Johan P. Warna CHEMICAL INDUSTRIES/137 FIFTH EDI T ION T h e C h e m i s t r y a n d T e c h n o l o g y o f P e t r o l e u m J a m e s G . S p e i g h t Boca Raton London New York CRC Press is an imprint of the Taylor & Francis Group, an informa business CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2014 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Version Date: 20130712 International Standard Book Number-13: 978-1-4398-7390-8 (eBook - PDF) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the valid- ity of all materials or the consequences of their use. 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Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com Contents Preface..........................................................................................................................................xxiii Author ............................................................................................................................................xxv Section i History, occurrence, and Recovery Chapter 1 History and Terminology .............................................................................................3 1.1 Historical Perspectives ......................................................................................3 1.2 Modern Perspectives .........................................................................................9 1.3 Definitions and Terminology ...........................................................................12 1.4 Native Materials ..............................................................................................14 1.4.1 Petroleum............................................................................................14 1.4.2 Opportunity Crudes and High-Acid Crudes ......................................15 1.4.3 Heavy Oil ...........................................................................................16 1.4.4 Foamy Oil ...........................................................................................16 1.4.5 Extra Heavy Oil ..................................................................................17 1.4.6 Bitumen ..............................................................................................17 1.4.7 Wax .....................................................................................................18 1.4.8 Asphaltite and Asphaltoid ..................................................................18 1.4.9 Bituminous Rock and Bituminous Sand ............................................19 1.4.10 Kerogen ..............................................................................................20 1.4.11 Natural Gas ........................................................................................20 1.5 Manufactured Materials ..................................................................................22 1.5.1 Wax .....................................................................................................22 1.5.2 Resid ...................................................................................................22 1.5.3 Asphalt ...............................................................................................23 1.5.4 Tar and Pitch ......................................................................................23 1.5.5 Coke ....................................................................................................24 1.5.6 Synthetic Crude Oil ............................................................................24 1.6 Derived Materials ............................................................................................24 1.6.1 Asphaltenes, Carbenes, and Carboids ................................................24 1.6.2 Resins and Oils ...................................................................................25 1.7 Oil Prices .........................................................................................................26 1.7.1 Pricing Strategies ...............................................................................26 1.7.2 Oil Price History ................................................................................27 1.7.3 Future of Oil .......................................................................................28 1.7.4 Epilogue..............................................................................................28 References ..................................................................................................................28 Chapter 2 Classification ..............................................................................................................31 2.1 Introduction .....................................................................................................31 2.2 Classification Systems .....................................................................................32 2.2.1 Classification as a Hydrocarbon Resource .........................................32 2.2.2 Classification by Chemical Composition ...........................................34 2.2.3 Correlation Index ................................................................................35 v © 2010 Taylor & Francis Group, LLC vi Contents 2.2.4 Density ...............................................................................................36 2.2.5 API Gravity .......................................................................................37 2.2.6 Viscosity ............................................................................................38 2.2.7 Carbon Distribution ...........................................................................38 2.2.8 Viscosity-Gravity Constant ...............................................................38 2.2.9 UOP Characterization Factor ............................................................39 2.2.10 Recovery Method ..............................................................................39 2.2.11 Pour Point ..........................................................................................40 2.3 Miscellaneous Systems ....................................................................................41 2.4 Reservoir Classification ...................................................................................42 2.4.1 Identification and Quantification .......................................................42 2.4.2 Future .................................................................................................44 References ..................................................................................................................44 Chapter 3 Origin and Occurrence ...............................................................................................47 3.1 Introduction .....................................................................................................47 3.2 Origin ..............................................................................................................47 3.2.1 Abiogenic Origin ...............................................................................48 3.2.2 Biogenic Origin .................................................................................49 3.2.2.1 Deposition of Organic Matter ............................................51 3.2.2.2 Establishment of Source Beds ...........................................51 3.2.2.3 Nature of the Source Material ...........................................53 3.2.2.4 Transformation of Organic Matter into Petroleum ............55 3.2.2.5 Accumulation in Reservoir Sediments ..............................57 3.2.2.6 In Situ Transformation of Petroleum .................................61 3.2.3 Differences between Abiogenic Theory and Biogenic Theory .........64 3.2.4 Relationship of Petroleum Composition and Properties....................65 3.3 Occurrence ......................................................................................................67 3.3.1 Reserves .............................................................................................67 3.3.2 Conventional Petroleum ....................................................................70 3.3.3 Natural Gas ........................................................................................71 3.3.4 Heavy Oil...........................................................................................72 3.3.5 Bitumen .............................................................................................73 References ..................................................................................................................75 Chapter 4 Reservoirs and Reservoir Fluids ................................................................................79 4.1 Introduction .....................................................................................................79 4.2 Reservoirs ........................................................................................................79 4.2.1 Structural Types ................................................................................80 4.2.2 Heterogeneity .....................................................................................81 4.3 Classes of Fluids ..............................................................................................82 4.4 Evaluation of Reservoir Fluids ........................................................................83 4.4.1 Sampling Methods .............................................................................84 4.4.2 Data Acquisition and QA/QC ............................................................85 4.5 Physical Composition and Molecular Weight .................................................87 4.5.1 Asphaltene Separation .......................................................................87 4.5.2 Fractionation ......................................................................................89 4.5.3 Molecular Weight ..............................................................................91 4.6 Reservoir Evaluation .......................................................................................95 References ..................................................................................................................96 © 2010 Taylor & Francis Group, LLC Contents vii Chapter 5 Kerogen ......................................................................................................................99 5.1 Introduction .....................................................................................................99 5.2 Properties .........................................................................................................99 5.3 Composition ...................................................................................................102 5.4 Classification .................................................................................................102 5.5 Isolation .........................................................................................................104 5.6 Methods for Probing Kerogen Structure .......................................................104 5.6.1 Ultimate (Elemental) Analysis .........................................................104 5.6.2 Functional Group Analysis...............................................................105 5.6.3 Oxidation ..........................................................................................105 5.6.4 Thermal Methods .............................................................................106 5.6.5 Acid-Catalyzed Hydrogenolysis .......................................................107 5.7 Structural Models ..........................................................................................107 5.8 Kerogen Maturation .......................................................................................109 References ................................................................................................................111 Chapter 6 Exploration, Recovery, and Transportation ..............................................................115 6.1 Introduction ...................................................................................................115 6.2 Exploration ....................................................................................................116 6.2.1 Gravity Methods ...............................................................................117 6.2.2 Magnetic Methods ............................................................................118 6.2.3 Seismic Methods ..............................................................................119 6.2.4 Electrical Methods ...........................................................................119 6.2.5 Electromagnetic Methods.................................................................120 6.2.6 Radioactive Methods ........................................................................120 6.2.7 Borehole Logging .............................................................................120 6.3 Drilling ..........................................................................................................121 6.3.1 Preparing to Drill .............................................................................121 6.3.2 Drilling Equipment ..........................................................................122 6.3.3 Drilling Rig ......................................................................................124 6.3.4 Drilling .............................................................................................125 6.4 Well Completion ............................................................................................125 6.5 Recovery ........................................................................................................126 6.5.1 Primary Recovery ............................................................................128 6.5.2 Secondary Recovery.........................................................................130 6.5.3 Enhanced Oil Recovery ...................................................................132 6.6 Products and Product Quality .......................................................................141 6.7 Transportation ...............................................................................................142 References ................................................................................................................147 Chapter 7 Recovery of Heavy Oil and Tar Sand Bitumen ........................................................149 7.1 Introduction ...................................................................................................149 7.2 Mining ...........................................................................................................153 7.2.1 Tar Sand Mining...............................................................................154 7.2.2 Hot-Water Process ............................................................................156 7.2.3 Other Processes ................................................................................158 7.3 Nonmining Methods ......................................................................................160 7.3.1 Steam-Based Processes ....................................................................161 7.3.2 Combustion Processes ......................................................................162 7.3.3 Other Processes ................................................................................165 © 2010 Taylor & Francis Group, LLC viii Contents 7.4 Upgrading during Recovery ..........................................................................173 7.4.1 Partial Upgrading at the Surface ......................................................174 7.4.1.1 Thermal Cracking Processes ............................................175 7.4.1.2 Solvent Processes ..............................................................176 7.4.2 Upgrading during In Situ Recovery .................................................176 7.4.2.1 Steam Distillation .............................................................177 7.4.2.2 Mild Thermal Cracking ....................................................177 7.4.2.3 Partial Combustion ...........................................................178 7.4.2.4 Solvent Deasphalting ........................................................180 7.4.2.5 Microbial Enhanced Oil Recovery ...................................181 7.4.3 Epilogue............................................................................................181 References ................................................................................................................182 Section ii composition and Properties Chapter 8 Chemical Composition .............................................................................................187 8.1 Introduction ...................................................................................................187 8.2 Ultimate (Elemental) Composition................................................................188 8.3 Chemical Composition ..................................................................................189 8.3.1 Hydrocarbon Components ................................................................190 8.3.1.1 Paraffin Hydrocarbons ......................................................191 8.3.1.2 Cycloparaffin Hydrocarbons (Naphthenes) ......................193 8.3.1.3 Aromatic Hydrocarbons ...................................................194 8.3.1.4 Unsaturated Hydrocarbons ...............................................196 8.3.2 Nonhydrocarbon Components ..........................................................196 8.3.2.1 Sulfur Compounds ............................................................197 8.3.2.2 Oxygen Compounds .........................................................198 8.3.2.3 Nitrogen Compounds ........................................................199 8.3.2.4 Metallic Constituents ........................................................201 8.3.2.5 Porphyrins .........................................................................202 8.4 Chemical Composition by Distillation ..........................................................203 8.4.1 Gases and Naphtha ...........................................................................205 8.4.2 Middle Distillates .............................................................................206 8.4.3 Vacuum Residua (1050°F+) ...............................................................208 References ................................................................................................................208 Chapter 9 Fractional Composition ............................................................................................211 9.1 Introduction ...................................................................................................211 9.2 Distillation .....................................................................................................212 9.2.1 Atmospheric Pressure .......................................................................216 9.2.2 Reduced Pressures ............................................................................216 9.2.3 Azeotropic and Extractive Distillation .............................................218 9.3 Solvent Treatment ..........................................................................................219 9.3.1 Asphaltene Separation ......................................................................221 9.3.1.1 Influence of Solvent Type ................................................221 9.3.1.2 Influence of the Degree of Dilution .................................224 © 2010 Taylor & Francis Group, LLC Contents ix 9.3.1.3 Influence of Temperature ...............................................224 9.3.1.4 Influence of Contact Time .............................................224 9.3.2 Fractionation ..................................................................................225 9.4 Adsorption .....................................................................................................227 9.4.1 Chemical Factors ...........................................................................227 9.4.2 Fractionation Methods ...................................................................228 9.4.2.1 General Methods ............................................................228 9.4.2.2 ASTM Methods .............................................................231 9.5 Chemical Methods .........................................................................................233 9.5.1 Acid Treatment ..............................................................................233 9.5.2 Molecular Complex Formation .....................................................235 9.5.2.1 Urea Adduction ..............................................................235 9.5.2.2 Thiourea Adduction .......................................................236 9.5.2.3 Adduct Composition ......................................................236 9.5.2.4 Adduct Structure ............................................................237 9.5.2.5 Adduct Properties ..........................................................237 9.6 Use of the Data ..............................................................................................238 References ................................................................................................................240 Chapter 10 Petroleum Analysis ...................................................................................................243 10.1 Introduction ...................................................................................................243 10.2 Petroleum Assay ............................................................................................243 10.3 Physical Properties ........................................................................................246 10.3.1 Elemental (Ultimate) Analysis ......................................................246 10.3.2 Density and Specific Gravity .........................................................247 10.3.3 Viscosity ........................................................................................249 10.3.4 Surface and Interfacial Tension .....................................................251 10.3.5 Metal Content ................................................................................253 10.3.6 Total Acid Number ........................................................................254 10.4 Thermal Properties ........................................................................................254 10.4.1 Volatility ........................................................................................255 10.4.2 Liquefaction and Solidification......................................................258 10.4.3 Carbon Residue .............................................................................260 10.4.4 Aniline Point .................................................................................261 10.4.5 Specific Heat ..................................................................................261 10.4.6 Latent Heat ....................................................................................262 10.4.7 Enthalpy or Heat Content ..............................................................262 10.4.8 Thermal Conductivity ...................................................................262 10.4.9 Pressure–Volume–Temperature Relationships ..............................263 10.4.10 Heat of Combustion .......................................................................263 10.4.11 Critical Properties ..........................................................................264 10.5 Electrical Properties ......................................................................................264 10.5.1 Conductivity ..................................................................................264 10.5.2 Dielectric Constant ........................................................................264 10.5.3 Dielectric Strength .........................................................................265 10.5.4 Dielectric Loss and Power Factor ..................................................265 10.5.5 Static Electrification ......................................................................266 10.6 Optical Properties .........................................................................................266 10.6.1 Refractive Index.............................................................................266 10.6.2 Optical Activity .............................................................................267 © 2010 Taylor & Francis Group, LLC