| Becker J.R. Crude oil waxes, emulsions, and asphaltenes. - Tulsa, Okla: Pennwell Books, 1997. - ix, 276 p.: ill. - ISBN 978-0-87814-737-3
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SECTION I Emulsions
Introduction .................................................... 3
1. Petroleum Companies and Emulsions ............................ 5
Oil and Water ................................................ 5
Emulsions .................................................... 6
Production Environments ...................................... 6
Specialty Chemicals and the Environment ...................... 8
Oil-in-Water Emulsions and Environmental Concerns ............ 8
Water-in-Oil Emulsions and Environmental Concerns ............ 9
Field Application of Emulsion Breakers ....................... 9
Specialized Equipment ....................................... 10
The Cost of Wet Oil ......................................... 12
The Cost of Oily Water ...................................... 14
Transport and Refining ...................................... 14
Refinery Influent Streams ................................... 15
Emulsion Formation .......................................... 16
Emulsion Formation Criteria ................................. 16
Solubility .................................................. 16
Intermediary Agents ......................................... 18
External and Internal Phase ................................. 21
Summary ..................................................... 26
2. Forces Involved in Emulsions ................................ 31
Chemical Complexities of Crude Oil Emulsions ................ 31
Nonpolar Interactions ....................................... 33
Combined Ionic and Inductive Forces ......................... 37
Aggregate Interactions ...................................... 37
Bipolar Partitioning ........................................ 41
Internal Phase Diffusion .................................... 41
Aggregate Number ............................................ 43
Emulsion Collision Frequency ................................ 44
Emulsion Collision Energy ................................... 46
Gravitational Settling Forces ............................... 46
Summary ..................................................... 47
3. Macroscopic Physical Behavior of Emulsions .................. 49
Viscosity ................................................... 49
Emulsion Behavior under Shear Stress ........................ 51
Temperature Effects on Emulsions ............................ 53
Gravitational Effects on Emulsions .......................... 55
Electromagnetic Field Effects on Emulsions .................. 56
Determination of Emulsion Type .............................. 60
Quantifying Phases .......................................... 60
Quantifying Phases: Oil-in-Water Emulsions .................. 60
Product Screening Methods ................................... 62
Oil in Water Emulsion Screening ............................. 64
Special Test Procedures ..................................... 64
Field Blending Practices .................................... 66
Summary ..................................................... 66
4. Oil Emulsion Breakers ....................................... 67
Water in Oil ................................................ 67
Xonionic Surfactants ........................................ 69
Nucleophiles ................................................ 77
Summary ..................................................... 80
5. Water Emulsion Breakers ..................................... 83
Oil in Water ................................................ 83
Organic Polysalt Emulsion Breakers .......................... 84
Idealized Organic Polysalts ................................. 84
Flocculation versus Emulsion Resolution ..................... 87
Water in Oil Emulsion Breakers .............................. 87
Oil in Water Emulsion Breakers .............................. 96
Polyamine and Quaternium Salts .............................. 96
Summary ..................................................... 98
SECTION II Waxes ........................................... 101
6. Petroleum Companies and Waxes .............................. 103
Paraffin Wax in Crude Oil .................................. 103
Paraffin Wax Production Problems ........................... 104
Organic Deposition Control ................................. 105
Removal of Paraffin Wax Deposits ........................... 105
Wax and Work-Over .......................................... 106
Physical and Mechanical Wax Control ........................ 106
Wax and Crude Oil Transport ................................ 107
Waxy Crude Oils and the Refinery ........................... 108
Treatment Problems ......................................... 108
Wax and Emulsions .......................................... 109
Solids and Waxes ........................................... 109
Waxes and Asphaltenes ...................................... 112
Some Wax Treatment Considerations .......................... 112
Testing Methodologies ...................................... 113
Summary .................................................... 122
7. Chemical Surfaces .......................................... 125
Wax Surfaces ............................................... 125
Surface Hierarchy .......................................... 126
Wax Defined ................................................ 126
Wax and Viscosity .......................................... 129
The Purity Gradient ........................................ 131
Wax and Changing Surfaces .................................. 134
Surface Tension and Wax .................................... 134
Wax Crystals ............................................... 138
Crystal Order .............................................. 138
Crystal Order and Surface Tension .......................... 140
Summary .................................................... 142
8. Wax Crystal Order and Temperature .......................... 145
The Odd Relationship of Time and Temperature ............... 145
Wax Crystal Habits ......................................... 147
London Forces and van der Waals Radii ...................... 147
Molecular Crystals ......................................... 147
Tern a it and Higher Eutectics ............................. 150
Introduction to a Kinetic Model ............................ 154
Crystal Modifiers .......................................... 156
A Return to a Kinetic Model ................................ 157
Gas Chromatographic Composition Profiles
Versus Kinetic Model .................................... 159
Summary .................................................... 161
9. Wax Physical Properties .................................... 165
Melting Point and Boiling Point of Alkanes ................. 165
Bulk System Properties ..................................... 167
Molecular Contributions to Bulk System Rheology ............ 167
Quantum Considerations of Viscosity ........................ 171
Intrinsic Viscosity ........................................ 175
Pseudoplasticity and Thixotropy ............................ 176
Yield Value ................................................ 176
Analogous Thermometry and Rheology ......................... 180
Sound As a Means of Measuring Aggregate Behavior ........... 180
Summary .................................................... 183
10.Wax and Quantum Effects .................................... 185
Electromagnetic Effects of Aggregation ..................... 185
Waxes and Piezoelectricity ................................. 189
Practical Applications of Electromagnetic
Aggregation Effects ..................................... 193
Molecular Collisions ....................................... 194
Taking Advantage of Crystallization ........................ 196
How Crystal Modifiers Work ................................. 196
Changes in Oystal Morphology ............................... 200
Crystal Modifier Products .................................. 200
Ciystal Modifier Applications .............................. 202
Crystal Modifier Synthetic Limitations ..................... 202
Some Wax Control Methods ................................... 203
Remedial Treatment Methods ................................. 203
Mechanical Methods ......................................... 205
Biotechnology .............................................. 205
Supplemental Methods of Wax Control ........................ 206
Summary .................................................... 206
SECTION III Asphaltenes ....................................... 209
11.Asphaltenes and Crude Oil .................................. 211
Asphaltene Deposits ........................................ 211
Coplaner Orbital Overlap or Pi Bonding ..................... 213
Polymeric Forms Derived from Protoporphyrin ................ 213
Solvation Sheaths .......................................... 215
Electrostatic Behavior of Asphaltenes ...................... 219
Asphaltene Destabiliztion .................................. 219
Unsheathed Asphaltene Cores ................................ 220
Metallocenes ............................................... 220
Magnetic Susceptibility and Streaming Potential ............ 222
External Aggregate Asphaltene Destabiliztion ............... 222
Summary .................................................... 224
12.Bulk Behavior of Asphaltenes ............................... 229
Operational Definitions Versus Chemical Composition ........ 229
Indirect Evidence for Asphaltene Composition ............... 230
Field Problems with Asphaltenes ............................ 230
Acid Effects on Asphaltenes ................................ 232
Artificial Causes of Asphaltene Deposition ................. 233
Oil Field Treatment Methods ................................ 233
Prochiction Factors Affecting Asphaltenc Deposition ........ 234
Asphaltene Deposition Control by Treatment
of Other Problems ....................................... 235
Fluid Transport Equipment .................................. 235
Summary .................................................... 236
13.Asphaltene Testing Methods ................................. 237
Solvent Testing ............................................ 237
Core Testing Procedures .................................... 238
Thin-Layer Photometry ...................................... 238
Size Exclusion Gel Permeation Chromatography ............... 240
Proposed Microwave Tests ................................... 240
Proposed Ligand Replacement Method ......................... 242
Designing Asphaltene Deposit Control Chemicals ............. 242
Chemical Handles ........................................... 244
Chemical Treatment Versus Reaction ......................... 246
Radical Reactions with Sulfur .............................. 248
Combination Product for Treatment of Asphaltenes ........... 248
Summary .................................................... 250
14.Physical Properties of Treating Chemicals .................. 251
Some Physical and Chemical Testing ......................... 251
Chemical Tests ............................................. 252
Physical Testing ........................................... 254
Specialized Testing Procedures ............................. 255
Summary .................................................... 255
Appendix A .................................................... 257
Appendix В .................................................... 259
Appendix С .................................................... 261
Index ......................................................... 267
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