Springer. Asphaltenes, Heavy Oils, and Petroleomics OLIVER C. MULLINS ERIC Y. SHEU AHMED HAMMAMI ALAN G. MARSHALL. Edited by

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1 Asphaltenes, Heavy Oils, and Petroleomics Edited by OLIVER C. MULLINS Scientific Advisor Schlumberger-Doll Research ERIC Y. SHEU Chief Scientist Vanton Research Laboratoiy, Inc. AHMED HAMMAMI New Venture Project Manager Schlumberger Oilfield Services and ALAN G. MARSHALL Robert O. Lawton Professor of Chemistry & Biochemistry Florida State University Springer

2 Contents 1. Petroleomics and Structure-Function Relations of Crude Oils and Asphaltenes Oliver C. Mullins 1 Introduction I 2 Evolution of the Oil Patch 5 3 Phenomological Petroleum Analysis 7 4 Petroleomics 10 5 Building Up Petroleum Science A Brief Outline 10 6 Asphaltenes: An Update of the Yen Model 13 7 Future Outlook in Petroleum Science 14 References Asphaltene Molecular Size and Weight by Time-Resolved Fluorescence Depolarization Henning Groenzin and Oliver C. Mullins 1 Introduction Overview Chemical Bonding of Functional Groups in Asphaltenes Techniques Employed to Study the Size of Asphaltenes Time-Resolved Fluorescence Depolarization (TRFD) The Optical Range Relevant to Asphaltene Investigations Structure Predictions from TRFD 26 2 Theory The Spherical Model The Anisotropic Rotator 30 3 Experimental Section Optics Methods Sample Preparation Solvent Resonant Quenching of Fluorescence 37 4 Results and Discussion Basic TRFD of Asphaltenes Many Virgin Crude Oil Asphaltenes and Sulfoxide Asphaltene Solubility Subfractions Asphaltenes and Resins Coal Asphaltenes versus Petroleum Asphaltenes Thermally Processed Feed Stock Alkyl-Aromatic Melting Points Asphaltene Molecular Structure 'Like your Hand' or 'Archipelago' 54 ix

3 X Contents 4.9 Considerations of the Fluorescence of Asphaltenes Asphaltene Molecular Diffusion; TRFD vs Other Methods 57 5 Conclusions 59 References Petroleomics: Advanced Characterization of Petroleum-Derived Materials by Fourier Transform ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) Ryan P. Rodgers and Alan G. Marshall 1 Introduction 63 2 FT-ICR MS Mass Accuracy and Mass Resolution Kendrick Mass and Kendrick Plots van Krevelen Diagrams DBE and Z Number ESI for Access to Polars EI, FD, and APPI for Access to Nonpolars 76 3 Molecular Weight Determination by Mass Spectrometry Low Molecular Weight for Petroleum Components Mass Spectrometry Caveats High Molecular Weight for Petroleum Components 83 4 Aggregation 84 5 Petroleomics 87 Acknowledgments 88 Glossary 89 References Molecular Orbital Calculations and Optical Transitions of PAHs and Asphaltenes Yosadara Ruiz-Morales 1 Introduction 95 2 Computational Details Results and Discussion Topological Characteristics of PAHs The HOMO-LUMO Optical Transition Aromaticity in PAHs and Asphaltenes: Application of the Y-rule The FAR Region in Asphaltenes Most Likely PAH Structural Candidates of the FAR Region in Asphaltenes from 5 to 10 Aromatic Rings Conclusions 135 Acknowledgments 135 References Carbon X-ray Raman Spectroscopy of PAHs and Asphaltenes Uwe Bergmann and Oliver C. Mullins 1 Introduction 139

4 Contents xi 2 Theory Experiment Results and Discussion Conclusion and Outlook 152 Acknowledgments 153 References Sulfur Chemical Moieties in Carbonaceous Materials Sudipa Mitra-Kirtley and Oliver C. Mullins 1 Introduction Carbonaceous Materials Production and Deposition of Organic Matter Diagenesis Sulfur in Carbonaceous Sediments Kerogen Formation Coal and Kerogen Macerals Catagenesis Asphaltene Fractions in Crude Oils X-Ray Absorption Near Edge Structure (XANES) Experimental Section Synchrotron Beamline Samples Least Squares Fitting Procedure Results and Discussions Sulfur XANES on Kerogens Sulfur XANES on Oil Fractions Sulfur K-Edge XANES on Coals Nitrogen XANES Conclusion 183 References Micellization Stig E. Friberg 1 Introduction Micelles in Aqueous Solutions Inverse Micellization in Nonpolar Media Asphaltene Association in Crude Oils Conclusions 201 Acknowledgments 202 References Insights into Molecular and Aggregate Structures of Asphaltenes Using HRTEM AtuI Sharma and Oliver C. Mullins 1 Introduction 205

5 xjj Contents 2 Theory of HRTEM and Image Analysis Basics of HRTEM Quantitative Information from TEM 212 Images 3 Experimental Section Samples 3.2 HRTEM Method Results and Discussion 2^ 5 Conclusions 227 Acknowledgments 228 References Ultrasonic Spectroscopy of Asphaltene Aggregation Gaelle Andreatta, Neil Bostrom, and Oliver C. Mullins 1 Introduction Ultrasonic Spectroscopy Ultrasonic Resonances Plane Wave Propagation Experimental Section Compressibility of Liquids and Ultrasonic Velocity Micellar Aggregation Model Theory Experimental Results on Surfactants Experimental Results on Asphaltenes Background Ultrasonic Determination of Various Asphaltenes Aggregation Properties Comparison of Experimental Results on UG8 Asphaltenes and Maltenes Differences Between Coal and Petroleum Asphaltenes Conclusion 255 References Asphaltene Self-Association and Precipitation in Solvents AC Conductivity Measurements Eric Sheu, Yicheng Long, and Hassan Hamza 1 Introduction Experimental Sample Instrument Measurement Theory Results Discussion and Conclusion Future Perspective 276 References 276

6 Contents xiii 11. Molecular Composition and Dynamics of Oils from Diffusion Measurements Denise E. Freed, Natalia V. Lisitza, Pabitra N. Sen, and Yi-Qiao Song 1 Introduction General Theory of Molecular Diffusion Experimental Method Mixtures of Alkanes Chain-Length Dependence Dependence on Mean Chain Length and Free Volume Model Comparison with Experiments Viscosity Discussion Dynamics Of Asphaltenes In Solution The Proton Spectrum of Asphaltene Solutions The Diffusion Constant and Diffusion Spectrum Discussion Conclusions 296 Acknowledgment 296 References Application of the PC-SAFT Equation of State to Asphaltene Phase Behavior P. David Ting, Doris L. Gonzalez, George J. Hirasaki, and Walter G. Chapman 1 Introduction 301 l. I Asphaltene Properties and Field Observations The Two Views of Asphaltene Interactions Our View and Approach Introduction to SAFT PC-SAFT Pure Component Parameters PC-SAFT Characterization of a Recombined Oil Comparison of Results and Analysis of Asphaltene Behavior Effect of Asphaltene Polydispersity 3 Summary on Phase Behavior 317 and Conclusions 323 Acknowledgments 324 References Application of Isothermal Titration Calorimetry in the Investigation of Asphaltene Association Daniel Merino-Garcia and Simon Ivar Andersen 1 Introduction The Concept of Micellization Experimental Asphaltene Separation Application of 1TC to Surfactants Nonaqueous Systems 334

7 xlv Contents 5 ITC Experiments with Asphaltene Solutions: Is There a CMC? Modeling ITC Experiments Application of ITC to Various Aspects of Asphaltene Association and Interaction with Other Substances Investigation of Asphaltene Subfractions Effect of Methylation of Asphaltenes Interaction of Asphaltene with Other Compounds Conclusions 350 Acknowledgments 350 References Petroleomics and Characterization of Asphaltene Aggregates Using Small Angle Scattering Eric Y. Sheu 1 Introduction Asphaltene Aggregation SAXS and SANS SAXS and SANS Instruments SAXS and SANS Experiments and Results SAXS Measurement on Ratawi Resin and Asphaltene SANS Measurement on Asphaltene Aggregation, Emulsion, and Dispersant Effect Discussion Conclusion Future Perspectives 373 Acknowledgments 373 References Self-Assembly of Asphaltene Aggregates: Synchrotron, Simulation and Chemical Modeling Techniques Applied to Problems in the Structure and Reactivity of Asphaltenes Russell Ft. Chianelli, Mohammed Siadati, Apurva Mehta, John Pople, Lante Carbognani Ortega, and Long Y Chiang 1 Introduction WAXS Synchrotron Studies and Sample Preparation SAXS Fractal Objects Scattering from Mass Fractal Objects Scattering from a Surface Fractal Object SAXS Studies of Venezuelan and Mexican Asphaltenes Self-Assembly of Synthetic Asphaltene Particles Conclusions 399 Acknowledgments 399 References 400

8 Contents xv 16. Solubility of the Least-Soluble Asphaltenes Jill S. Buckley, Jianxin Wang, and Jefferson L. Creek 1 Introduction Importance of the Least-Soluble Asphaltenes Detection of the Onset of Asphaltene Instability Asphaltenes as Colloidal Dispersions Asphaltenes as Lyophilic Colloids Solubility of Large Molecules Solubility Parameters Flory-Huggins Predictions: The Asphaltene Solubility Model (ASM) Asphaltene Instability Trends (ASIST) ASIST Established by Titrations with n-alkanes Use of ASIST to Predict Onset Pressure Asphaltene Stability in Oil Mixtures Some Remaining Problems Effect of Temperature on ASIST Polydispersity and Amount of Asphaltene Wetting, Deposition, and Coprecipitation Model Systems and Standards Conclusions 427 Acknowledgment 427 References Dynamic Light Scattering Monitoring of Asphaltene Aggregation in Crude Oils and Hydrocarbon Solutions Igor K. Yudin and Mikhail A. Anisimov 1 Introduction Dynamic Light Scattering Technique Aggregation of Asphaltenes in Toluene-Heptane Mixtures Aggregation of Asphaltenes in Crude Oils Stabilization of Asphaltene Colloids Viscosity and Microrheology of Petroleum Systems Conclusions 465 Acknowledgment 466 References Near Infrared Spectroscopy to Study Asphaltene Aggregation in Solvents Kyeongseok Oh and Milind D. Deo 1 Introduction Literature Experimental 472

9 xv; Contents 4 Results and Discussion Asphaltene Aggregation or Self-Association Onset of Asphaltene Precipitation Effect of the Solvent Asphaltene Subfractions Conclusions 486 Acknowledgments 487 References Phase Behavior of Heavy Oils John M. Shaw and Xlangyang Zou 1 Introduction Origin of Multiphase Behavior in Hydrocarbon Mixtures Phase Behavior Prediction Bulk Phase Behavior Prediction for Hydrocarbon Mixtures Asphaltene Precipitation and Deposition Models Experimental Methods and Limitations Phase Behavior Observations and Issues Heavy Oil Heavy Oil + Solvent Mixtures Phase Behavior Reversibility Conclusions 506 Acknowledgments 507 References Selective Solvent Deasphalting for Heavy Oil Emulsion Treatment Yicheng Long, Tadeusz Dabros, and Hassan Hamza 1 Introduction Bitumen Chemistry Stability of Water-in-Bitumen Emulsions In situ Bitumen Emulsion and Bitumen Froth Size Distributions of Emulsified Water Droplets and Dispersed Solids Stabilization Mechanism of Bitumen Emulsions Effect of Solvent on Bitumen Emulsion Stability Treatment of Bitumen Emulsions with Aliphatic Solvents Behavior of Bitumen Emulsion upon Dilution Settling Characteristics of Bitumen Emulsions Diluted with Aliphatic Solvent Settling Curve and Settling Rate of WD/DS/PA Aggregates Structural Parameters of WD/DS/PA Aggregates Measuring Settling Rate of WD/DS/PA Aggregates Using In-Line Fiber-Optic Probe Asphaltene Rejection Product Quality Water and Solids Contents Product Quality Micro-Carbon Residue (MCR) Product Quality Metals Contents 542

10 Contents xvii 5.10 Product Quality Sulfur and Nitrogen Contents Viscosity of Bitumen Conclusion 543 Acknowledgments 545 References The Role of Asphaltenes in Stabilizing Water-in-Crude Oil Emulsions Johan Sjdblom, Pil V. Hemmingsen, and Harald Kallevik 1 Introduction Chemistry ofcrude Oils and Asphaltenes Analytical Separation of Crude Oil Components Solubility and Aggregation of Asphaltenes Characterization of Crude Oils by Near Infrared Spectroscopy Asphaltene Aggregation Studied by High-Pressure NIR Spectroscopy Disintegration of Asphaltenes Studied by NIR Spectroscopy Asphaltene Aggregation Studied by NMR Adsorption of Asphaltenes and Resins Studied by Dissipative Quartz Crystal Microbalance (QCM-D) Interfacial Behavior and Elasticity of Asphaltenes Chemistry of Naphthenic Acids Origin and Structure Phase Equilibria Water-in-Crude Oil Emulsions Stability Mechanisms Characterization by Critical Electric Fields Multivariate Analysis and Emulsion Stability High-Pressure Performance of W/O Emulsions 578 Acknowledgments 584 References Live Oil Sample Acquisition and Downhole Fluid Analysis Go Fujisawa and Oliver C. Mullins 1 Introduction Wireline Fluid Sampling Tools Downhole Fluid Analysis with Wireline Tools Measurement Physics DFA Implementation in Wireline Tools Live Oil Sampling Process Contamination Phase Transition Chain of Custody "What Is the Nature of the Hydrocarbon Fluid?" "What Is the Size and Structure of the Hydrocarbon-Bearing Zone?" Conclusions 614 References 615

11 xviii Contents 23. Precipitation and Deposition of Asphaltenes Systems: A Flow Assurance Overview Ahmed Hammami and John Ratulowski in Production 1 Introduction Chemistry of Petroleum Fluids Saturates Aromatics Resins Asphaltenes Petroleum Precipitates and Deposits Petroleum Waxes Asphaltene Deposits Diamondoids Gas Hydrates Terminology: Precipitation vs. Deposition Mechanisms of Asphaltene Precipitation: What We think We Know and Why? Colloidal Model Effect of Compositional Change Effect of Pressure Change The de Boer Plot Reversibility of Asphaltene Precipitation Sampling Laboratory Sample Handling and Analyses Sample Handling and Transfer Compositional Analyses Oil-Based Mud (OBM) Contamination Quantification Dead Oil Characterization Dead Oil Asphaltene Stability Tests Live Oil Asphaltene Stability Techniques Light Transmittance (Optical) Techniques High Pressure Microscope (HPM) Deposition Measurements Asphaltene Precipitation Models 652 Acknowledgment 656 References 656 Index 661