Analytical Advances for Hydrocarbon Research

1. Estimation of Physical Properties and Composition of Hydrocarbon Mixtures.- 1. Introduction.- 2. Pure Hydrocarbons.- 2.1 Generalized Correlations for Physical Properties.- 2.2 Properties of Heavy Hydrocarbons.- 3 Properties of Petroleum Fractions.- 4. Composition of Petroleum Fractions.- 4.1 Characterization Parameters for Molecular Type.- 4.2 Development of Predictive Methods.- 4.3 Prediction of Sulfur Content and Carbon Residue.- 5. Summary.- 6. Nomenclature.- 7. References.- 2. Advances in Elemental Analysis of Hydrocarbon Products.- 1. Introduction.- 2. Atomic Absorption Spectrometry (AAS).- 2.1 Graphite Furnace Atomic Absorption Spectrometry (GFAAS).- 3. Inductively Coupled Plasma Atomic Emission Spectrometry (ICPAES).- 4. Inductively Coupled Plasma Mass Spectrometry (ICP/MS).- 5. Overview of Atomic Spectroscopic Methods.- 6. Ion Chromatography (IC).- 7. Microelemental Analysis.- 8. Neutron Activation Analysis (NAA).- 8.1 Radiochemical NAA.- 9. X-ray Fluorescence (XRF).- 10. Analysis of Used Oils.- 11. Sulfur.- 12. Concluding Remarks.- 13. References.- 3. Selective Detection of Sulfur and Nitrogen Compounds in Low Boiling Petroleum Streams by Gas Chromatography.- 1. Background.- 2. Sulfur Compounds in Light Streams.- 2.1 Instrumentation.- 2.2 Sulfur Chemiluminescence Detection System.- 2.3 Gas Chromatography.- 2.4 Identification of Sulfur Compounds.- 2.5 Quantitation of Sulfur Compounds.- 3. Nitrogen Compounds in Light Streams.- 3.1 Instrumentation.- 3.2 Principle of Nitrogen Chemiluminescence Detection.- 3.3 Gas Chromatography.- 3.4 Quantitation of Nitrogen Compounds.- 4. Future Work.- 5. References.- 4. Molecular Characterization of Petroleum and Its Fractions by Mass Spectrometry.- 1. Introduction.- 2. Low ResolutionlHigh Ionizing Voltage Mass Spectrometric Analysis.- 3. High Resolution Mass Spectrometry.- 4. Gas Chromatography-Mass Spectrometry (GC-MS).- 5. Liquid Chromatography-Mass Spectrometry (LC-MS).- 6. Future Trends.- 7. References.- 5. Thin-Layer Chromatography for Hydrocarbon Characterization in Petroleum Middle Distillates.- 1. Analysis of Petroleum Middle Distillates.- 2. Introduction to Modem Thin-Layer Chromatography (TLC).- 2.1 Advantages of TLC for the Analysis of Complex Mixtures.- 2.2 Previous Research Done on TLC of Petroleum Products.- 3. Materials, Methods and TLC Systems Used in this Research.- 3.1 Samples Analyzed.- 3.2 Stationary Phases.- 3.3 Preparation of Berberine-Impregnated Silica Gel Plates.- 3.4 Application of Samples.- 3.4.1 Automatic Sample Spotter.- 3.4.2 Band-sprayer Sample Applicator.- 3.5 Elution of Samples.- 3.5.1 Conventional Vertical Elution.- 3.5.2 Horizontal Developing Chamber.- 3.6 Detection by Densitometry.- 3.7 TLC Systems Used.- 3.7.1 Conventional TLC System.- 3.7.2 High-Efficiency TLC System.- 3.8 Quantification.- 3.8.1 Preparative TLC.- 3.9 Validation of Results.- 4. Application of TLC to Characterization of Middle Distillates.- 4.1 Phenomenon of Fluorescence Induced by Berberine in TLC.- 4.2 HTA of Middle Distillates Using Conventional TLC System.- 4.3 HTA of Gas Oils Using High-Efficiency TLC System.- 5. Conclusions and Future Trends.- 6. Acknowledgements.- 7. References.- 6. Chromatographic Analysis of Fuels.- 1. Analysis of Naphthasl Motor Gasolines by Gas Chromatography.- 1.1 Introduction.- 1.2 Classification of GC Methods for Naphtha Analysis.- 1.3 Terminology.- 1.4 Single Capillary Methods.- 1.5 "Pressurized" Naphtha Samples.- 1.6 Multidimensional Methods.- 1.7 Combination of Micropackedl/Packed PIONA and Single Capillary Column Analyses.- 1.8 Capillary Column Multidimensional Systems.- 1.9 Comprehensive Two-dimensional GC (2D-GC).- 1.10 Other GC Methods for Blended Gasoline Analysis.- 2. Analyses of Naphtha, Motor Gasolines, Jet Fuels, Diesel Fuels and Higher Petroleum Fractions by Supercritical Fluid Chromatography (SFC) and Liquid Chromatography (LC).- 2.1 Supercritical Fluid Chromatography (gasolines, jet fuels and diesel fuels).- 2.2 High Performance Liquid Chromatography (HPLC) for Higher Boiling Petroleum Fractions (Lube FeedslProducts, Vacuum Gas Oils).- 2.3 High Performance Liquid Chromatography (HPLC) for Lower Boiling Petroleum Fractions (Jet Fuels, Diesels).- 2.4 Characterization of High Boiling Petroleum Fractions by Thin Layer Chromatography with FlO Detection (TLC-FID).- 3. References.- 7. Temperature-Programmed Retention Indices for GC and GC-MS of Hydrocarbon Fuels and Simulated Distillation GC of Heavy Oils.- 1. Introduction.- 2. Experimental.- 2.1 Reagents and Fuels.- 2.2 Retention Index.- 2.3 Chromatographic Separation of Distillate Fuels.- 2.4 Solvent Extraction of Petroleum Resids.- 2.5 High-temperature Simulated Distillation GC.- 2.6 Quantitative Calculations from SimDis GC Data.- 2.7 Hydroprocessing of Resids.- 3. Results and Discussion.- 3.1 GC and GC-MS of Distillate Fuels.- 3.1.1 Retention Index of Model Compounds.- 3.1.2 Temperature Dependence of Retention Index.- 3.1.3 Dependence of Retention Index on Polarity of GC Column.- 3.1.4 Characterization of JP-8 Jet Fuels Using RI.- 3.1.5 Potential Applications of Temperature-Programmed RI.- 3.2 SimDis GC and GC-MS of Middle Distillate Fuels.- 3.3 High-Temperature SimDis GC for Petroleum Resids.- 3.3.1 High-Temperature SimDis GC Method.- 3.3.2 HT-SimDis GC Analysis of Resids.- 3.3.3 Analysis of Upgraded Products.- 4. Conclusions.- 5. Acknowledgements.- 6. References.- 8. Mass Spectrometric Analyses for Elemental Sulfur and Sulfur Compounds in Petroleum Products and Crude Oils.- 1. Introduction.- 2. Analysis for Elemental Sulfur by Mass Spectrometry-Mass Spectrometry.- 3. Analysis of Thiophenic Compounds in Petroleum Streams by Mass Spectrometry-Mass Spectrometry.- 4. Monitoring Thioaromatics in Refinery Processes.- 5. Monitoring Reaction Products of Elemental Sulfur with Hydrocarbons.- 6. Summary.- 7. References.- 9. Biomarker Analysis in Petroleum Exploration.- 1. Introduction.- 2. Biological Markers in Oils.- 3. Biomarker Analysis by GC and GC-MS.- 4. GC-MS-MS Analysis of Steranes.- 5. Principal Component Analysis of GC-MS and GC-MS-MS Data.- 6. Future Prospectives.- 7. References.- 10. Applications of Light Hydrocarbon Molecular and Isotopic Compositions in Oil and Gas Exploration.- 1. Introduction.- 2. Methods of Analysis.- 2.1 Gas Chromatography of Light Hydrocarbons (C2-C9+).- 2.2 C6-C7 Chromatographic Separations.- 2.3 Compound Specific Isotopic Analysis (CSIA).- 3. Applications of Light Hydrocarbons to Petroleum Systems Analysis.- 3.1 Thermal Maturity.- 3.2 Oil-eondensate Correlations.- 3.3 Thermochemical Sulfate Reduction (TSR).- 4. Future Directions.- 5. Acknowledgements.- 6. References.- 11. Coupling MassSpectrometry with Liquid Chromatography for Hydrocarbon Research.- 1. Introduction.- 2. Mass Spectrometry Review.- 3. LC-MS Interfaces.- 3.1 Moving Belt (MB) Interface.- 3.2 Thermospray (TSP).- 3.3 Electrospray (ESP).- 3.4 Atmospheric Pressure Chemical Ionization (APCI).- 4. Homologous Z-Series for Elemental Composition Determination.- 5. LC-MS for Petroleum Fractions.- 5.1 Saturates.- 5.2 Aromatics.- 5.3 Polars.- 5.4 Resids.- 6. Future Trends.- 7. References.- 12. Advanced Molecular Characterization by Mass Spectrometry: Applications for Petroleum and Petrochemicals.- 1. Introduction.- 2. Application Areas.- 3. Crude Assays.- 3.1 Unseparated Fractions.- 3.2 Whole Crude Oils.- 3.3 Saturated Hydrocarbon Fractions.- 3.4 Aromatic Hydrocarbon Fractions.- 3.5 Olefins.- 4. Corrosion.- 4.1 Sulfur Compound Types.- 4.2 Organic Acids.- 4.3 Nitrogen Compounds.- 5. Additives and Contaminants.- 6. Asphalts and Non-Boiling Fractions.- 7. Polymers and Residues.- 8. Conclusion and Future Challenges.- 9. References.- 13. Chromatographic Separation and Atmospheric Pressure IonizationlMass Spectrometric Analysis of Nitrogen, Sulfur and Oxygen Containing Compounds in Crude Oils.- 1. NSO Compounds in Crude Oil.- 2. General Separation Methods for Crude Oil and Related Products.- 2.1 Distillation.- 2.2 Adsorption Chromatography.- 2.3 High Performance Liquid Chromatography.- 2.4 Mass Spectrometry.- 3. Methods for NSO Compounds.- 3.1 Separation of Acids.- 3.2 Atmospheric Pressure IonizationlMass Spectrometry of Naphthenic Acids.- 3.3 Separation of Nitrogen and Oxygen Compounds.- 3.4 Atmospheric Pressure IonizationlMass Spectrometry of Nitrogen-containing Compounds.- 3.5 Separation of Organosulfur Compounds.- 3.6 Atmospheric Pressure IonizationlMass Spectrometry of Organosulfur Compounds.- 4. Acknowledgements.- 5. References.- 14. Characterization of Heavy Oils and Heavy Ends.- 1. Introduction.- 2. Heavy OilslHeavy Ends Separation and Characterization Schemes.- 2.1 Chemical Methods.- 2.1 Hyphenated Techniques.- 2.3 Selective/Specific Element Detection.- 2.4 Fraction Separation.- 2.5 Mathematical Algorithms.- 2.6 Other Characterization Schemes for HC, XHC and Heavy Ends.- 3. Illustrative Examples on the Characterization of HC. XHC and Heavy Ends.- 3.1 SARA Group-type Analysis.- 3.2 Studies on XHC and Isolated ABAN Fractions. One Application of Average Molecular Representations.- 3.3 Estimation of Crude Oil and Heavy Ends Quality Parameters Using Neural Network Algorithms.- 4. Conclusions.- 5. Acknowledgements.- 6. Glossary of Frequent Referred Terms.- 7. References.- 15. Advances in NMR Techniques for Hydrocarbon Characterization.- 1. Introduction.- 2. Discussion.- 2.1 Availability of Higher Magnetic Field Strengths Provides Increased Sensitivity and Resolution.- 2.2 Improvements in Sensitivity form Higher Magnetic Fields and New Probe Designs Facilitate Further Development of On-line Coupling with Separation Techniques.- 2.3"Chromatography in a NMR Tube": - Spectral Editing with Pulsed Field Gradient (PFG) Techniques Improves Analysis of Hydrocarbon Mixtures.- 3. Conclusions and Future Prospects.- 4. Acknowledgements.- 5. References.- 16. Analysis of Polymeric Hydrocarbon Materials by Matrix-Assisted LaserDesorption/Ionization (MALDI) MassSpectrometry.- 1. Introduction.- 2. MALDI-MS.- 2.1 Overview.- 2.2 Sample Preparation.- 2.3 DesorptionlIonizationProcess.- 2.4 Mass Analyzer.- 2.5 Advantages of Using MALDI.- 2.6 Matrix Requirements.- 2.7 MALDI and Nonpolar Analytes.- 2.8 Analyte/Matrix Miscibility.- 2.9 Solvents.- 2.10 Cationization of Polymers in MALDI.- 3. Synthetic Polymers as MALDI Analytes.- 3.1 Polymer Distribution.- 4. Matrices for Polymer Analysis.- 4.1 Nonpolar Matrices.- 4.2 Nonpolar Matrices with Cationization Reagents.- 4.3 Ag vs. Cu Cationizatin Reagents.- 5. Conclusions.- 6. References.- 17. LaserDesorption/Ionization (LDI)- and MALDI-Fourier Transform Ion Cyclotron Resonance MassSpectrometric (FTI/ICR/MS) Analysis of Hydrocarbon Samples.- 1. Introduction.- 2. FTI/ICR/MS Overview.- 2.1 Fundamentals of Ion Motion.- 2.2 Experimental Sequence.- 3. LDI-FT/ICR/MS Analysis of Porphyrins.- 3.1 Sample Preparation.- 3.2 Thin Films.- 3.3 Crystalline Sample Preparation.- 4. MALDI-FT/ICR/MS Analysis of Nonpolar Analytes.- 5. Acknowledgements.- 6. References.- 18. X-Ray Absorption Spectroscopy for the Analysis of Hydrocarbons and Their Chemistry.- 1. Introduction.- 2. X-ray Absorption Spectroscopy: Theoretical Background.- 2.1 Extended X-ray Absorption Fine Structure (EXAFS).- 2.2 X-ray Absorption Near Edge Structure (XANES).- 3. Experimental Techniques.- 4. XANES Spectroscopy and Microspectroscopy at the Carbon K-Edge.- 5. Sulfur-Crosslinks in Rubber.- 6. Catalyst for Hydrocarbon Synthesis and Catalytic Reactions.- 7. Acknowledgement.- 8. References.