Asphaltenes, Heavy Oils, and Petroleomics Book

Petroleomics and Structure-Function Relations of Crude Oils and Asphaltenes   Oliver C. Mullins
Introduction     1
Evolution of the Oil Patch     5
Phenomological Petroleum Analysis     7
Petroleomics     10
Building Up Petroleum Science-A Brief Outline     10
Asphaltenes: An Update of the Yen Model     13
Future Outlook in Petroleum Science     14
References     16
Asphaltene Molecular Size and Weight by Time-Resolved Fluorescence Depolarization   Henning Groenzin   Oliver C. Mullins
Introduction     17
Overview     17
Chemical Bonding of Functional Groups in Asphaltenes     18
Techniques Employed to Study the Size of Asphaltenes     18
Time-Resolved Fluorescence Depolarization (TRFD)     21
The Optical Range Relevant to Asphaltene Investigations     22
Structure Predictions from TRFD     26
Theory     27
The Spherical Model     27
The Anisotropic Rotator     30
Experimental Section     33
Optics Methods     33
Sample Preparation     35
Solvent Resonant Quenching of Fluorescence     37
Results and Discussion     39
Basic TRFD of Asphaltenes     39
Many Virgin Crude Oil Asphaltenes-and Sulfoxide     43
Asphaltene Solubility Subfractions     43
Asphaltenes and Resins     45
Coal Asphaltenes versus Petroleum Asphaltenes     45
Thermally Processed Feed Stock     50
Alkyl-Aromatic Melting Points     53
Asphaltene Molecular Structure 'Like your Hand' or 'Archipelago'     54
Considerations of the Fluorescence of Asphaltenes     56
Asphaltene Molecular Diffusion; TRFD vs Other Methods     57
Conclusions     59
References     60
Petroleomics: Advanced Characterization of Petroleum-Derived Materials by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS)   Ryan P. Rodgers   Alan G. Marshall
Introduction     63
FT-ICR MS     65
Mass Accuracy and Mass Resolution     67
Kendrick Mass and Kendrick Plots     68
van Krevelen Diagrams     73
DBE and Z Number     75
ESI for Access to Polars     75
EI, FD, and APPI for Access to Nonpolars     76
Molecular Weight Determination by Mass Spectrometry     78
Low Molecular Weight for Petroleum Components     79
Mass Spectrometry Caveats     82
High Molecular Weight for Petroleum Components     83
Aggregation     84
Petroleomics     87
Acknowledgments     88
Glossary     89
References     89
Molecular Orbital Calculations and Optical Transitions of PAHs and Asphaltenes   Yosadara Ruiz-Morales
Introduction     95
Computational Details     100
Results and Discussion     102
Topological Characteristics of PAHs     103
The HOMO-LUMO Optical Transition     106
Aromaticity in PAHs and Asphaltenes: Application of the Y-rule     119
The FAR Region in Asphaltenes     124
Most Likely PAH Structural Candidates of the FAR Region in Asphaltenes from 5 to 10 Aromatic Rings     127
Conclusions     135
Acknowledgments     135
References     135
Carbon X-ray Raman Spectroscopy of PAHs and Asphaltenes   Uwe Bergmann   Oliver C. Mullins
Introduction     139
Theory     142
Experiment     143
Results and Discussion     145
Conclusion and Outlook     152
Acknowledgments     153
References      153
Sulfur Chemical Moieties in Carbonaceous Materials   Sudipa Mitra-Kirtley   Oliver C. Mullins
Introduction     157
Carbonaceous Materials     159
Production and Deposition of Organic Matter     159
Diagenesis     160
Sulfur in Carbonaceous Sediments     161
Kerogen Formation     162
Coal and Kerogen Macerals     162
Catagenesis     164
Asphaltene Fractions in Crude Oils     165
X-Ray Absorption Near Edge Structure (XANES)     165
Experimental Section     168
Synchrotron Beamline     168
Samples     169
Least Squares Fitting Procedure     171
Results and Discussions     172
Sulfur XANES on Kerogens     174
Sulfur XANES on Oil Fractions     175
Sulfur K-Edge XANES on Coals     176
Nitrogen XANES     178
Conclusion     183
References     184
Micellization   Stig E. Friberg
Introduction     189
Micelles in Aqueous Solutions     190
Inverse Micellization in Nonpolar Media     194
Asphaltene Association in Crude Oils     199
Conclusions      201
Acknowledgments     202
References     202
Insights into Molecular and Aggregate Structures of Asphaltenes Using HRTEM   Atul Sharma   Oliver C. Mullins
Introduction     205
Theory of HRTEM and Image Analysis     208
Basics of HRTEM     208
Quantitative Information from TEM Images     212
Experimental Section     218
Samples     218
HRTEM Method     218
Results and Discussion     219
Conclusions     227
Acknowledgments     228
References     228
Ultrasonic Spectroscopy of Asphaltene Aggregation   Gaelle Andreatta   Neil Bostrom   Oliver C. Mullins
Introduction     231
Ultrasonic Spectroscopy     233
Ultrasonic Resonances     234
Plane Wave Propagation     235
Experimental Section     236
Compressibility of Liquids and Ultrasonic Velocity     238
Micellar Aggregation Model     238
Theory     238
Experimental Results on Surfactants     241
Experimental Results on Asphaltenes     247
Background     247
Ultrasonic Determination of Various Asphaltenes Aggregation Properties     248
Comparison of Experimental Results on UG8 Asphaltenes and Maltenes     253
Differences Between Coal and Petroleum Asphaltenes     254
Conclusion     255
References     255
Asphaltene Self-Association and Precipitation in Solvents-AC Conductivity Measurements   Eric Sheu   Yicheng Long   Hassan Hamza
Introduction     259
Experimental     264
Sample     264
Instrument     264
Measurement     265
Theory     266
Results     269
Discussion and Conclusion     274
Future Perspective     276
References     276
Molecular Composition and Dynamics of Oils from Diffusion Measurements   Denise E. Freed   Natalia V. Lisitza   Pabitra N. Sen   Yi-Qiao Song
Introduction     279
General Theory of Molecular Diffusion     280
Experimental Method     282
Mixtures of Alkanes     283
Chain-Length Dependence     284
Dependence on Mean Chain Length and Free Volume Model     285
Comparison with Experiments     287
Viscosity     289
Discussion      291
Dynamics Of Asphaltenes In Solution     292
The Proton Spectrum of Asphaltene Solutions     292
The Diffusion Constant and Diffusion Spectrum     293
Discussion     294
Conclusions     296
Acknowledgment     296
References     296
Application of the PC-SAFT Equation of State to Asphaltene Phase Behavior   P. David Ting   Doris L. Gonzalez   George J. Hirasaki   Walter G. Chapman
Introduction     301
Asphaltene Properties and Field Observations     302
The Two Views of Asphaltene Interactions     303
Our View and Approach     305
Introduction to SAFT     306
PC-SAFT Pure Component Parameters     307
PC-SAFT Characterization of a Recombined Oil     307
Comparison of Results and Analysis of Asphaltene Behavior     313
Effect of Asphaltene Polydispersity on Phase Behavior     317
Summary and Conclusions     323
Acknowledgments     324
References     325
Application of Isothermal Titration Calorimetry in the Investigation of Asphaltene Association   Daniel Merino-Garcia   Simon Ivar Andersen
Introduction     329
The Concept of Micellization     330
Experimental     331
Asphaltene Separation     331
Application of ITC to Surfactants     332
Nonaqueous Systems     334
ITC Experiments with Asphaltene Solutions: Is There a CMC?     335
Modeling ITC Experiments     338
Application of ITC to Various Aspects of Asphaltene Association and Interaction with Other Substances     340
Investigation of Asphaltene Subfractions     341
Effect of Methylation of Asphaltenes     343
Interaction of Asphaltene with Other Compounds     345
Conclusions     350
Acknowledgments     350
References     351
Petroleomics and Characterization of Asphaltene Aggregates Using Small Angle Scattering   Eric Y. Sheu
Introduction     353
Asphaltene Aggregation     355
SAXS and SANS     356
SAXS and SANS Instruments     362
SAXS and SANS Experiments and Results     364
SAXS Measurement on Ratawi Resin and Asphaltene     365
SANS Measurement on Asphaltene Aggregation, Emulsion, and Dispersant Effect     367
Discussion     371
Conclusion     372
Future Perspectives      373
Acknowledgments     373
References     373
Self-Assembly of Asphaltene Aggregates: Synchrotron, Simulation and Chemical Modeling Techniques Applied to Problems in the Structure and Reactivity of Asphaltenes   Russell R. Chianelli   Mohammed Siadati   Apurva Mehta   John Pople   Lante Carbognani Ortega   Long Y. Chiang
Introduction     375
WAXS Synchrotron Studies and Sample Preparation     377
SAXS     380
Fractal Objects     381
Scattering from Mass Fractal Objects     383
Scattering from a Surface Fractal Object     383
SAXS Studies of Venezuelan and Mexican Asphaltenes     383
Self-Assembly of Synthetic Asphaltene Particles     393
Conclusions     399
Acknowledgments     399
References     400
Solubility of the Least-Soluble Asphaltenes   Jill S. Buckley   Jianxin Wang   Jefferson L. Creek
Introduction     401
Importance of the Least-Soluble Asphaltenes     402
Detection of the Onset of Asphaltene Instability     403
Asphaltenes as Colloidal Dispersions     403
Asphaltenes as Lyophilic Colloids     405
Solubility of Large Molecules      405
Solubility Parameters     406
Flory-Huggins Predictions: The Asphaltene Solubility Model (ASM)     412
Asphaltene Instability Trends (ASIST)     414
ASIST Established by Titrations with n-Alkanes     414
Use of ASIST to Predict Onset Pressure     417
Asphaltene Stability in Oil Mixtures     420
Some Remaining Problems     424
Effect of Temperature on ASIST     425
Polydispersity and Amount of Asphaltene     425
Wetting, Deposition, and Coprecipitation     426
Model Systems and Standards     426
Conclusions     427
Acknowledgment     427
References     428
Asphaltene Onset Detection by Batch Titration     429
Historical Interpretations of n-Alkane Titration Data     432
Calculation of Solubility Parameters Using PVTsim     432
Oil and Asphaltene Properties     434
Prediction of Live Oil Asphaltene Stability from ASIST     436
Dynamic Light Scattering Monitoring of Asphaltene Aggregation in Crude Oils and Hydrocarbon Solutions   Igor K. Yudin   Mikhail A. Anisimov
Introduction     439
Dynamic Light Scattering Technique     441
Aggregation of Asphaltenes in Toluene-Heptane Mixtures     448
Aggregation of Asphaltenes in Crude Oils     454
Stabilization of Asphaltene Colloids     460
Viscosity and Microrheology of Petroleum Systems     462
Conclusions     465
Acknowledgments     466
References     466
Near Infrared Spectroscopy to Study Asphaltene Aggregation in Solvents   Kyeongseok Oh   Milind D. Deo
Introduction     469
Literature     470
Experimental     472
Results and Discussion     473
Asphaltene Aggregation or Self-Association     473
Onset of Asphaltene Precipitation     475
Effect of the Solvent     479
Asphaltene Subfractions     485
Conclusions     486
Acknowledgments     487
References     487
Phase Behavior of Heavy Oils   John M. Shaw   Xiangyang Zou
Introduction     489
Origin of Multiphase Behavior in Hydrocarbon Mixtures     490
Phase Behavior Prediction     493
Bulk Phase Behavior Prediction for Hydrocarbon Mixtures     493
Asphaltene Precipitation and Deposition Models     494
Experimental Methods and Limitations      495
Phase Behavior Observations and Issues     497
Heavy Oil     497
Heavy Oil + Solvent Mixtures     500
Phase Behavior Reversibility     504
Conclusions     506
Acknowledgments     507
References     507
Selective Solvent Deasphalting for Heavy Oil Emulsion Treatment   Yicheng Long   Tadeusz Dabros   Hassan Hamza
Introduction     511
Bitumen Chemistry     512
Stability of Water-in-Bitumen Emulsions     515
In situ Bitumen Emulsion and Bitumen Froth     515
Size Distributions of Emulsified Water Droplets and Dispersed Solids     516
Stabilization Mechanism of Bitumen Emulsions     518
Effect of Solvent on Bitumen Emulsion Stability     519
Treatment of Bitumen Emulsions with Aliphatic Solvents     522
Behavior of Bitumen Emulsion upon Dilution     522
Settling Characteristics of Bitumen Emulsions Diluted with Aliphatic Solvent     524
Settling Curve and Settling Rate of WD/DS/PA Aggregates     526
Structural Parameters of WD/DS/PA Aggregates     531
Measuring Settling Rate of WD/DS/PA Aggregates Using In-Line Fiber-Optic Probe     534
Asphaltene Rejection     537
Product Quality-Water and Solids Contents     538
Product Quality-Micro-Carbon Residue (MCR)     540
Product Quality-Metals Contents     542
Product Quality-Sulfur and Nitrogen Contents     542
Viscosity of Bitumen     543
Conclusion     543
Acknowledgments     545
References     545
The Role of Asphaltenes in Stabilizing Water-in-Crude Oil Emulsions   Johan Sjoblom   Pal V. Hemmingsen   Harald Kallevik
Introduction     549
Chemistry of Crude Oils and Asphaltenes     551
Analytical Separation of Crude Oil Components     551
Solubility and Aggregation of Asphaltenes     554
Characterization of Crude Oils by Near Infrared Spectroscopy     555
Asphaltene Aggregation Studied by High-Pressure NIR Spectroscopy     556
Disintegration of Asphaltenes Studied by NIR Spectroscopy     559
Asphaltene Aggregation Studied by NMR     563
Adsorption of Asphaltenes and Resins Studied by Dissipative Quartz Crystal Microbalance (QCM-D)     563
Interfacial Behavior and Elasticity of Asphaltenes     566
Chemistry of Naphthenic Acids     569
Origin and Structure     570
Phase Equilibria      570
Water-in-Crude Oil Emulsions     572
Stability Mechanisms     572
Characterization by Critical Electric Fields     573
Multivariate Analysis and Emulsion Stability     574
High-Pressure Performance of W/O Emulsions     578
Acknowledgments     584
References     584
Live Oil Sample Acquisition and Downhole Fluid Analysis   Go Fujisawa   Oliver C. Mullins
Introduction     589
Wireline Fluid Sampling Tools     591
Downhole Fluid Analysis with Wireline Tools     593
Measurement Physics     593
DFA Implementation in Wireline Tools     601
Live Oil Sampling Process     604
Contamination     604
Phase Transition     606
Chain of Custody     607
"What Is the Nature of the Hydrocarbon Fluid?"     608
"What Is the Size and Structure of the Hydrocarbon-Bearing Zone?"     610
Conclusions     614
References     615
Precipitation and Deposition of Asphaltenes in Production Systems: A Flow Assurance Overview   Ahmed Hammami   John Ratulowski
Introduction     617
Chemistry of Petroleum Fluids     619
Saturates      621
Aromatics     621
Resins     621
Asphaltenes     622
Petroleum Precipitates and Deposits     622
Petroleum Waxes     622
Asphaltene Deposits     623
Diamondoids     623
Gas Hydrates     623
Terminology: Precipitation vs. Deposition     624
Mechanisms of Asphaltene Precipitation: What We Think We Know and Why?     625
Colloidal Model     626
Effect of Compositional Change     626
Effect of Pressure Change     628
The de Boer Plot     630
Reversibility of Asphaltene Precipitation     631
Sampling     631
Laboratory Sample Handling and Analyses     634
Sample Handling and Transfer     634
Compositional Analyses     635
Oil-Based Mud (OBM) Contamination Quantification     635
Dead Oil Characterization     637
Dead Oil Asphaltene Stability Tests     640
Live Oil Asphaltene Stability Techniques     643
Light Transmittance (Optical) Techniques     643
High Pressure Microscope (HPM)     647
Deposition Measurements     651
Asphaltene Precipitation Models      652
Acknowledgment     656
References     656
Index     661