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Full Description
Determining the composition and properties of complex hydrocarbon mixtures in petroleum, synthetic fuels, and petrochemical products usually requires a battery of analytical techniques that detect and measure specific features of the molecules, such as boiling point, mass, nuclear magnetic resonance frequencies, etc. there have always been a need for new and improved analytical technology to better understand hydrocarbon chemistry and processes. This book provides an overview of recent advances and future challenges in modern analytical techniques that are commonly used in hydrocarbon applications. Experts in each of the areas covered have reviewed the state of the art, thus creating a book that will be useful to readers at all levels in academic, industry, and research institutions.
Contents
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.
