ANALYTICALADVANCES FORHYDROCARBON

RESEARCH

MODERN ANALYTICAL CHEMISTRY

ADVANCES IN COAL SPECTROSCOPYEdited by Henle L. C. Meuzelaar

ANALYTICAL ADVANCES FOR HYDROCARBON RESEARCHEdited by Chang Samuel Hsu

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ANALYTICAL ADVANCES FOR HYDROCARBON

RESEARCH

Edited by

CHANG SAMUEL HSU ExxanMabil Research and Engineering Ca.

Batan Rauge, Louisiana

SPRINGER-SCIENCE+BUSINESS MEDIA, LLC

Library of Congress Cataloging-in-Publication Data

Hsu, Chang Samuel. Analytical advances for hydrocarbon researchJedited by Chang Samuel Hsu,

p. cm. - (Modem analytical chemistry) ISBN 978-1-4613-4840-5 ISBN 978-1-4419-9212-3 (eBook) DOI 10.1007/978-1-4419-9212-3

1. Hydrocarbons-Research. 2. Petroleum-Analysis. 1. Title. II. Series.

TP691 .H77 2003 665.5-dc21

ISBN 978-1-4613-4840-5

©2003 Springer-Science+Business Media New York Originally published by Kluwer Academic I Plenum Publishers, New York in 2003 Softcover reprint ofthe hardcover Ist edition 2003

W 9 8 7 6 5 4 3 2 I

A C.1.P. record for this book is available from the Library of Congress

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2002040700

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permis sion from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work

Contributors

Druzual, Jenny

Cameron, A. S.

Carbognani, Lante

Cebolla, V. L.

Chawla, Dirbal

Colaiocco, Silvia

Di Sanzo, Frank P.

Domingo, M. P.

Espidel, Joussef

Fedora, J . W.

Fitzgerald, W. P.

Galvez, E. M.

Analytical ChemistryDepartment, PDVSA Intevep,P.O. Box 76343 Caracas 1070-A Venezuela

Research Department, Productsand ChemicalsDivisionImperial Oil,Samia, Ontario, Canada,N7T 8C8

PDVSA-INTEVEP. P.O. Box 76343. Caracas 1070A.Venezuela

Instituto de Carboquimica, ConsejoSuperiorde InvestigacionesCientificas (CSIC), P.O. Box 589, 50080 Zaragoza, Spain

ExxonMobil Research & Engineering, PaulsboroTechnicalCenter, Paulsboro, NewJersey 08066

PDVSA-INTEVEP. P.O. Box 76343. Caracas 1070 A.Venezuela

ExxonMobil Research & Engineering Co.Annandale, NewJersey USA

Institutode Carboquimica, ConsejoSuperiorde InvestigacionesCientificas(CSIC), P.O. Box 589, 50080Zaragoza, Spain

PDVSA-INTEVEP. P.O. Box 76343. Caracas 1070 A.Venezuela

Research Department, Productsand Chemicals DivisionImperial Oil, Samia, Ontario, Canada, N7T 8C8

Research Department, Productsand ChemicalsDivisionImperial Oil, Samia, Ontario,Canada,N7T 8C8

Institutode Carboquimica, Consejo Superiorde InvestigacionesCientificas(CSIC), P.O. Box 589, 50080 Zaragoza,Spain

v

vi Contributors

Hormes, Josef Center for Advanced Microstructures and Devices (CAMD)Louisiana State University, Baton Rouge, LA 70806

Hsu, Chang Samuel ExxonMobil Research and Engineering Co.,Baton Rouge, LA 07821

Isaksen, Gary H. ExxonMobil Upstream Research Co., Houston, TX 77252

Kennedy, Gordon J. ExxonMobil Research and Engineering Company,1545 Route 22 East, Annandale, NJ 08801

Lai, Wei-Chuan Department of Energy & Geo-Environmental Engineering,The Pennsylvania State University, University Park, PA 16802

Limbach, Patrick A. Department of Chemistry, University of Cincinnati,Cincinnati, OH 45221

Macha, Stephen F. Department of Chemistry, University of Cincinnati,Cincinnati, OH 45221

Matt, M. Instituto de Carboquimica, Consejo Superior de InvestigacionesCientificas (CSIC), P.O. Box 589, 50080 Zaragoza, Spain

Membrado, L. Instituto de Carboquimica, Consejo Superior de InvestigacionesCientificas (CSIC), P.O. Box 589,50080 Zaragoza, Spain

Mendez, Aaron Analytical Chemistry Department, PDVSA Intevep,P.O. Box 76343 Caracas 1070-A Venezuela

Modrow, Hartwig Institute of Physics, Bonn University, Nussallee 12, D-53115Bonn, Germany

Nadkarni, R. A. Kishore Millennium Analytics, Inc., East Brunswick, NJ 08816

Nero, Vincent P. ChevronTexaco, 3901 Briarpark, Houston, Texas 77042

Peters, Kenneth E. ExxonMobil Upstream Research Co., Houston, TX 77252

Proulx, R. Research Department, Products and Chemicals DivisionImperial Oil, Samia, Ontario, Canada, N7T 8C8

Reddy, K. Madhusudan Department of Energy & Geo-Environmental Engineering,The Pennsylvania State University, University Park, PA 16802

Riazi, M. R. Department of Chemical Engineering, Kuwait University,P.O.Box 5969, Safat 13060, Kuwait

Robins, Chad L. Department of Chemistry, University of Cincinnati,Cincinnati, OH 45221

Roussis, S. G. Research Department, Products and Chemicals DivisionImperial Oil, Samia, Ontario, Canada, N7T 8C8

Rudzinski, Walter E. Department of Chemistry, Southwest Texas State University,San Marcos, Texas 78666

Schaps, M. ExxonMobil Upstream Research Co., Houston, TX 77252

Contributors

Song, Chunshan

Vandell, Victor E.

Walters, Clifford C.

Wei, Boli

vii

Department of Energy& Geo-Environmental Engineering,The Pennsylvania StateUniversity, University Park,PA 16802

Analytical Science Division, Hercules IncorporatedWilmington, DE. 19808

ExxonMobii Research and Engineering Co.Annandale, NJ 0880I

Department of Energy& Gee-Environmental Engineering,The Pennsylvania State University, University Park, PA 16802

Preface

Petroleum and fossil fuels (coal, oil shale, etc.) consist of complexhydrocarbon mixtures. Hydrocarbon research has been playing an importantrole in all phases of the petroleum business. In the upstream, hydrocarbonfingerprints can provide clues for oil/gas potential in basin assessments. Thedistribution of some specific hydrocarbons, so called biomarkers, can be usedfor the assessment of source input, age, maturity and alteration of oils. In thedownstream, the studies of molecular transformation of hydrocarbons(including heteroatom-containing) in various processes would help thedesign and improvement of petroleum refining and utilization. Thecompositional analysis of the products provides important information onquality and performance. In the environmental area, the understanding ofhydrocarbon degradation in nature would help the clean-up effort afteraccidental release of petroleum and its refined products into the environment.The properties and processibility of petroleum and its fractions are closelyrelated to the composition . Hence, in hydrocarbon research analyticalcharacterization has been playing important roles in the determination ofcomposition and the understanding of compositional changes during refiningand other chemical processes .

There have always been constant needs for new and improved analyticaltechnology for a better analysis of petroleum composition . At the 220thAmerican Chemical Society (ACS) National Meeting in Washington, DC onAugust 20-24, 2000,. there was a symposium in the Division of PetroleumChemistry dedicated to analytical characterization of petroleum and itsfractions. This book is based on the material given at the symposium andextends its scope to broadly cover recent advances in the analytical arena.We are fortunate to have many experts who agree to contribute articles intheir respective areas of expertise. Each article will give brief review, recentdevelopments and future perspectives of the area covered.

To determine the composition of complex petroleum mixtures, it usuallyrequires a battery of analytical techniques that detect and measure specific

ix

x Preface

features of the molecules, such as mass, boiling point, vibrationalfrequencies, nuclear magnetic resonance frequencies, etc. This book isintended to broadly cover modem analytical techniques that are commonlyused to determine the petroleum composition for upstream, downstream,petrochemical and environmental applications.

The analytical areas covered include physical property measurement andestimation, elemental analysis, chromatography, mass spectrometry (MS),nuclear magnetic resonance (NMR) spectroscopy, and x-ray absorptionspectroscopy. In recent years many of these analytical techniques arecombined, or "hyphenated", to take advantages of the unique features of eachtechnique.

Chapter I presents characterization methods and estimation ofthermodynamic and physical properties of hydrocarbon and petroleumfractions through the use some easily measurable properties. Chapter 2overviews elemental composition analysis by a variety of instruments. Manyof ASTM methods based on instrumental elemental analysis are described.

Prior separations of petroleum into its fractions by boiling point orpolarity facilitate subsequent analysis by spectroscopies. Lowerboiling petroleum fractions are normally separated by gaschromatography (GC), while higher boiling fractions by liquidchromatography (LC) or supercritical fluid chromatography (SFC). Inpetroleum, sulfur and nitrogen-containing compounds are important becauseof processing and environmental concerns. Chapter 3 describes sulfur- andnitrogen-specific detection when a hydrocarbon mixture or a petroleumfraction is analyzed directly by Gc. Complex hydrocarbon mixtures can beanalyzed by high- and low-resolution MS for compound type distributions.This is described in Chapter 4. This chapter also describes recentdevelopments in combined gas chromatography-mass spectrometry (GC-MS)for hydrocarbon analysis. An ingenious method of using thin-layerchromatography (TLC) for hydrocarbon type analysis of middle distillates isreported in Chapter 5, particularly the use of berberine-impregnated silicaplate for the detection of saturated hydrocarbons by fluorescence.

Chapter 6 describes the analyses of fuels using GC, SFC, highperformance liquid chromatography (HPLC) and TLC. The use of 2­dimensional GC for fuel analysis is briefly introduced. Chapter 7 selectivelyreviews temperature-programmed retention indices for GC and GC-MSanalysis of distillate fuels, and high temperature simulated distillation GCanalysis of residual oils and their upgraded products. Chapter 8 focuses onthe analysis of sulfur species, including elemental sulfur, using MS, tandemmass spectrometry (MS-MS), and GC-MS.

Chromatography and mass spectrometry have also been widely appliedin upstream research . Chapter 9 describes the applications of GC-MS andGC-MS-MS for the characterization of petroleum biomarkers . Achemometric approach has been used to retrieve important geochemicalinformation from the data set. Chapter 10 gives a comprehensive review ofthe light hydrocarbons in petroleum geochemistry. Their molecular and

Preface xi

isotropic compositions have been applied to thennal maturity determination,oil-condensate correlation and thermal sulfate reduction.

There are many new analytical techniques developed during the lastdecade to characterize high boiling and heavy hydrocarbons and petroleumfractions. Chapter 11 describes the coupling of liquid chromatography andmass spectrometry (LC-MS) for molecular-level characterization ofsaturates, aromatics, polars and resids. Chapter 12 illustrates the uses ofadvanced mass spectrometric methods for solving challenging analyticalproblems in refineries and chemical plants of the petroleum industry.Chapter 13 discusses the fractionation of crude oils, particularly nitrogen-,sulfur- and oxygen-containing (NSO) compounds that are analyzed byatmospheric pressure chemical ionization (APCI), an method for LC-MScharacterization of high boiling and heavy petroleum fractions. Chapter 14reviews and discusses the characterization schemes and strategies for heavycrude oils and heavy fractions (heavy ends) of crude oils, includingfractionation, chromatographic separations, and molecular, microscopic andx-ray spectroscopic analyses. Chapter 15 highlights some of the recentimprovements in nuclear magnetic resonance (NMR) instrumentation thatimpacts on hydrocarbon characterization, such as higher magnetic fields,facile implementation of pulsed gradient and on-line coupling withchromatography (such as HPLC-NMR, SFC-NMR, etc.)

Chapters 16 and 17 broadly cover the use of matrix-assisted laserdesorption/ionization (MALDI) for heavy hydrocarbons and hydrocarbonpolymers. For analyzing non-polar hydrocarbon materials, applications ofnon-polar matrices with cationization agents have been developed that aredifferent than conventional MALDI in ionization mechanisms. Morediscussions of laser desorption/ionization and the utilization of ultrahigh­resolution Fourier-transform ion cyclotron resonance mass spectrometers(FT/ICR/MS) are introduced in Chapter 17. Chapter 18 reviews theapplications of x-ray absorption spectroscopy, particularly x-ray absorptionfine structure (XAFS), extended XAFS (EXAFS) and x-ray near edgestructure (XANES), for the characterization of heavy hydrocarbon matrices,polymers/rubbers and hydrocarbon synthesis catalysts.

I would like to thank all of the authors for their contributions. I am alsograteful to the reviewers for their valuable comments and for their precioustime. I sincerely hope this book will become a useful reference to not onlyexperienced researchers, but also new comers and graduate students who areactive in hydrocarbon research. I wish to thank ExxonMobil Research andEngineering for supporting my research. Last but not least, to my wife GraceMiao-miao Chen, for her understanding and support of my time and effort inediting this book.

Chang Samuel HsuEditor

CONTENTS

1. Estimation of Physical Properties and Composition ofHydrocarbon MixturesM. R. Raizi

1. Introduction 12 Pure Hydrocarbons 4

2.1 Generalized Correlations for Physical Properties 52.2 Properties of Heavy Hydrocarbons 8

3 Properties of Petroleum Fractions 104. Composition of Petroleum Fractions 14

4.1 Characterization Parameters for Molecular Type 154.2 Development of Predictive Methods 184.3 Prediction of Sulfur Content and Carbon Residue 20

5. Summary 226. Nomenclature 237. References. ..... 24

2. Advances in Elemental Analysis of Hydrocarbon ProductsR. A. Kishore Nadkarni

1. Introduction 272. Atomic Absorption Spectrometry (AAS) 32

2.1 Graphite Furnace Atomic Absorption Spectrometry(GFAAS) 34

3. Inductively Coupled Plasma Atomic Emission Spectrometry(ICPAES) 35

4. Inductively Coupled Plasma Mass Spectrometry (ICP/MS) 385. Overview of Atomic Spectroscopic Methods 416. Ion Chromatography (IC) 427. Microelemental Analysis 438. Neutron Activation Analysis (NAA) 44

xiii

xiv Contents

8.1 Radiochemical NAA 459. X-ray Fluorescence (XRF) 4610. Analysis of Used Oils 4911. Sulfur 5112. Concluding Remarks 5313. References 54

3. Selective Detection of Sulfur and Nitrogen Compounds in LowBoiling Petroleum Streams by Gas ChromatographyBirbal Chawla

1. Background... ..... 572. Sulfur Compounds in Light Streams 58

2.1 Instrumentation 592.2 Sulfur Chemiluminescence Detection System 602.3 Gas Chromatography ...................................................... 612.4 Identification of Sulfur Compounds 622.5 Quantitation of Sulfur Compounds 65

3. Nitrogen Compounds in Light Streams 663.1 Instrumentation 663.2 Principle of Nitrogen Chemiluminescence Detection.... 673.3 Gas Chromatography...................................................... 673.4 Quantitation of Nitrogen Compounds 71

4. Future Work .. 715. References 71

4. Molecular Characterization of Petroleum and Its Fractions byMass SpectrometryAaron Mendez and Jenny Bruzual

1. Introduction 732. Low ResolutionlHigh Ionizing Voltage Mass Spectrometric

Analysis 743. High Resolution Mass Spectrometry 774. Gas Chromatography-Mass Spectrometry (GC-MS) 815. Liquid Chromatography-Mass Spectrometry (LC-MS) 856. Future Trends 877. References 90

5. Thin-Layer Chromatography for Hydrocarbon Characterization inPetroleum Middle DistillatesV. L. Cebolla, L. Membrado , M. Matt, E. M. Galvez and M. P. Domingo

Contents xv

1. Analysis of Petroleum Middle Distillates 952. Introduction to Modem Thin-Layer Chromatography (TLC) 97

2.1 Advantages of TLC for the Analysis of ComplexMixtures 98

2.2 Previous Research Done on TLC of PetroleumProducts 99

3. Materials, Methods and TLC Systems Used in this Research 1003.1 Samples Analyzed 1003.2 Stationary Phases 1003.3 Preparation of Berberine-Impregnated Silica Gel

Plates 1003.4 Application of Samples 100

3.4.1 Automatic Sample Spotter 1003.4.2 Band-sprayer Sample Applicator 101

3.5 Elution of Samples 1013.5.1 Conventional Vertical Elution 1013.5.2 Horizontal Developing Chamber 101

3.6 Detection by Densitometry 1023.7 TLC Systems Used 102

3.7.1 Conventional TLC System 1023.7.2 High-Efficiency TLC System 102

3.8 Quantification 1023.8.1 Preparative TLC 103

3.9 Validation of Results 1034. Application of TLC to Characterization of Middle Distillates.... 103

4.1 Phenomenon of Fluorescence Induced by Berberine inTLC 103

4.2 HTA of Middle Distillates Using Conventional TLCSystem 105

4.3 HTA of Gas Oils Using High-Efficiency TLC System.. 1085. Conclusions and Future Trends 1116. Acknowledgements 1117. References 112

6. Chromatographic Analysis of FuelsFrank P. Di Sanzo

1. Analysis of NaphthaslMotor Gasolines by GasChromatography 113

1.1 Introduction 1131.2 Classification of GC Methods for Naphtha Analysis 1141.3 Terminology.... ............................................................... 1151.4 Single Capillary Methods 115

xvi Contents

1.5 "Pressurized" Naphtha Samples ........... .......................... 1181.6 Multidimensional Methods ............................................ 1201.7 Combination of MicropackedlPacked PlaNA and

Single Capillary Column Analyses .......................... 1261.8 Capillary Column Multidimensional Systems ............... 1271.9 Comprehensive Two-dimensional GC (2D-GC) ............ 1321.10 Other GC Methods for Blended Gasoline Analysis ....... 133

2. Analyses of Naphtha, Motor Gasolines, Jet Fuels, Diesel Fuelsand Higher Petroleum Fractions by Supercritical FluidChromatography (SFC) and Liquid Chromatography (LC) 134

2.1 Supercritical Fluid Chromatography (gasolines, jetfuels and diesel fuels) .............................................. 134

2.2 High Performance Liquid Chromatography (HPLC)for Higher Boiling Petroleum Fractions (LubeFeedslProducts, Vacuum Gas Oils) ......................... 138

2.3 High Performance Liquid Chromatography (HPLC)for Lower Boiling Petroleum Fractions (Jet Fuels,Diesels) ................................................ .................... 141

2.4 Characterization of High Boiling Petroleum Fractionsby Thin Layer Chromatography with FlODetection (TLC-FID) ............................................... 142

3. References ................................................................................... 144

7. Temperature-Programmed Retention Indices for GC and GC·MS ofHydrocarbon Fuels and Simulated Distillation GC of Heavy OilsChunshan Song, Wei-Chuan Lai, K. Madhusudan Reddy and Boli Wei

1. Introduction 1472. Experimental 151

2.1 Reagents and Fuels 1512.2 Retention Index 1512.3 Chromatographic Separation of Distillate Fuels 1522.4 Solvent Extraction of Petroleum Resids 1532.5 High-temperature Simulated Distillation GC 1532.6 Quantitative Calculations from SimDis GC Data 1542.7 Hydroprocessing of Resids 155

3. Results and Discussion 1563.1 GC and GC-MS of Distillate Fuels 156

3.1.1 Retention Index of Model Compounds 1563.1.2 Temperature Dependence of Retention Index... 1623.1.3 Dependence of Retention Index on Polarity of

GC Column 1683.1.4 Characterization of JP-8 Jet Fuels Using RI 171

Contents xvii

3.1.5 Potential Applications of Temperature-Programmed RI............................................ 176

3.2 SimDis GC and GC-MS of Middle Distillate Fuels 1783.3 High-Temperature SimDis GC for Petroleum Resids 193

3.3.1 High-Temperature SimDis GC Method 1933.3.2 HT-SimDis GC Analysis of Resids 1973.3.3 Analysis of Upgraded Products 200

4. Conclusions 2055. Acknowledgements 2076. References 207

8. Mass Spectrometric Analyses for Elemental Sulfur and SulfurCompounds in Petroleum Products and Crude OilsVincent P. Nero

1. Introduction 2112. Analysis for Elemental Sulfur by Mass Spectrometry-Mass

Spectrometry 2123. Analysis of Thiophenic Compounds in Petroleum Streams by

Mass Spectrometry-Mass Spectrometry.... ........................... 2144. Monitoring Thioaromatics in Refinery Processes 2175. Monitoring Reaction Products of Elemental Sulfur with

Hydrocarbons 2206. Summary ..................................................................................... 2227. References 222

9. Biomarker Analysis in Petroleum ExplorationC. S. Hsu, C. C. Walters, G. H. Isaksen, M. E. Schaps and K. E. Peters

1. Introduction 2232. Biological Markers in Oils 2253. Biomarker Analysis by GC and GC-MS 2334. GC-MS-MS Analysis of Steranes 2385. Principal Component Analysis of GC-MS and GC-MS-MS

Data 2426. Future Prospectives 2437. References 245

10. Applications of Light Hydrocarbon Molecular and IsotopicCompositions in Oil and Gas ExplorationClifford C. Walters, Gary H. Isaksen and Kenneth E. Peters

1. Introduction 247

xviii Contents

2. Methods of Analysis 2492.1 Gas Chromatography of Light Hydrocarbons (CrC9+) .. 2502.2 C6-C7 Chromatographic Separations 2522.3 Compound Specific Isotopic Analysis (CSIA) 254

3. Applications of Light Hydrocarbons to Petroleum SystemsAnalysis 256

3.1 Thermal Maturity 2573.2 Oil-eondensate Correlations 2603.3 Thermochemical Sulfate Reduction (TSR) 261

4. Future Directions 2635. Acknowledgements 2646. References 264

11. Coupling MassSpectrometry withLiquid Chromatography forHydrocarbon ResearchChang Samuel Hsu

1. Introduction " 2672. Mass Spectrometry Review 2693. LC-MS Interfaces 270

3.1 Moving Belt (MB) Interface 2703.2 Thermospray (TSP) 2723.3 Electrospray (ESP) 2723.4 Atmospheric Pressure Chemical Ionization (APCI) 273

4. Homologous Z-Series for Elemental CompositionDetermination 273

5. LC-MS for Petroleum Fractions 2735.1 Saturates 2745.2 Aromatics 2745.3 Polars 2805.4 Resids 281

6. Future Trends 2827. References 283

12. Advanced Molecular Characterization by MassSpectrometry:Applications for Petroleum and PetrochemicalsS. G. Roussis, J. W. Fedora, W P. Fitzgerald. A. S. Cameron andR. Proulx

1. Introduction 2852. Application Areas 2863. Crude Assays 287

3.1 Unseparated Fractions 287

Contents xix

3.2 Whole Crude Oils 288~.3 Saturated Hydrocarbon Fractions 2903.4 Aromatic Hydrocarbon Fractions 2913.5 Olefins 295

4. Corrosion 2974.1 Sulfur Compound Types 2974.2 Organic Acids 2984.3 Nitrogen Compounds 300

5. Additives and Contaminants 3016. Asphalts and Non-Boiling Fractions 3057. Polymers and Residues 3068. Conclusion and Future Challenges 3089. References 310

13. Chromatographic Separation and Atmospheric PressureIonizationlMass Spectrometric Analysis of Nitrogen, Sulfur andOxygen Containing Compounds in Crude OilsWalter E. Rudzinski

1. NSO Compounds in Crude Oil 3132. General Separation Methods for Crude Oil and Related

Products 3142.1 Dist illation 3142.2 Adsorption Chromatography .......................................... 3152.3 High Performance Liquid Chromatography ........ 3172.4 Mass Spectrometry 317

3. Methods for NSO Compounds 3203.1 Separation of Acids 3203.2 Atmospheric Pressure IonizationlMass Spectrometry

of Naphthenic Acids 3233.3 Separation of Nitrogen and Oxygen Compounds 3253.4 Atmospheric Pressure IonizationlMass Spectrometry

of Nitrogen-containing Compounds 3263.5 Separation of Organosulfur Compounds 3273.6 Atmospheric Pressure IonizationlMass Spectrometry

of Organosulfur Compounds 3304. Acknowledgements 3335. References 333

14. Characterization of Heavy Oils and Heavy EndsLante Carbognani, JoussejEspidel and Silvia Colaiocco

1. Introduction 337

xx Contents

2. Heavy OilslHeavy Ends Separation and CharacterizationSchemes 340

2.1 Chemical Methods 3412.1 Hyphenated Techniques 3422.3 Selective/Specific Element Detection 3442.4 Fraction Separation 3452.5 Mathematical Algorithms 3472.6 Other Characterization Schemes for HC, XHC and

Heavy Ends 3493. Illustrative Examples on the Characterization of HC. XHC and

Heavy Ends 3513.1 SARA Group-type Analysis 3523.2 Studies on XHC and Isolated ABAN Fractions. One

Application of Average MolecularRepresentations 355

3.3 Estimation of Crude Oil and Heavy Ends QualityParameters Using Neural Network Algorithms 359

4. Conclusions 3625. Acknowledgements 3626. Glossary of Frequent Referred Terms 3627. References 363

15. Advances in NMR Techniques for Hydrocarbon CharacterizationGordon J. Kennedy

1. Introduction 3692. Discussion 370

2.1 Availability of Higher Magnetic Field StrengthsProvides Increased Sensitivity and Resolution ........ 370

2.2 Improvements in Sensitivity form Higher MagneticFields and New Probe Designs FacilitateFurther Development of On-line Couplingwith Separation Techniques 371

2.3 "Chromatography in a NMR Tube": - Spectral Editingwith Pulsed Field Gradient (PFG) TechniquesImproves Analysis of Hydrocarbon Mixtures 374

3. Conclusions and Future Prospects 3834. Acknowledgements 3835. References 383

Contents XXI

16. Analysis of Polymeric Hydrocarbon Materials by Matrix-AssistedLaserDesorption/lonization (MALDI) MassSpectrometryStephen F. Macha and Patrick A. Limbach

1. Introduction 3852. MALDI-MS 386

2.1 Overview................................................. ....................... 3862.2 Sample Preparation 3862.3 DesorptionlIonizationProcess 3862.4 Mass Analyzer 3872.5 Advantages of Using MALDI 3892.6 Matrix Requirements 3902.7 MALDI and Nonpolar Analytes 3912.8 Analyte/MatrixMiscibility........ ..................................... 3912.9 Solvents 3922.10 Cationization of Polymers in MALDI 393

3. Synthetic Polymers as MALDI Analytes 3953.1 Polymer Distribution 395

4. Matrices for Polymer Analysis 3964.1 Nonpolar Matrices 3974.2 Nonpolar Matrices with CationizationReagents 3984.3 Ag vs. Cu Cationizatin Reagents 401

5. Conclusions 4026. References 403

17. LaserDesorption/lonization (LDI)- and MALDI-Fourier TransformIon Cyclotron Resonance MassSpectrometric (FTIICRlMS)Analysis of Hydrocarbon SamplesChad L Robins, Stephen F. Macha, Victor E. Vandell, and Patrick A.Limbach

1. Introduction 4052. FTIICRIMS Overview................................................................. 405

2.1 Fundamentals of Ion Motion 4052.2 Experimental Sequence 408

3. LDI-FTIICR/MS Analysis of Porphyrins 4093.1 Sample Preparation 4093.2 Thin Films :......................... ................................ 4093.3 Crystalline Sample Preparation 413

4. MALDI-FTIICR/MS Analysis of NonpolarAnalytes 4155. Acknowledgements 4196. References 419

xxii Contents

18. X-Ray Absorption Spectroscopy for the Analysis of Hydrocarbonsand Their ChemistryJosef Hormes and Hartwig Modrow

1. Introduction 4212. X-ray Absorption Spectroscopy: Theoretical Background 425

2.1 Extended X-ray Absorption Fine Structure (EXAFS) ... 4252.2 X-ray Absorption Near Edge Structure (XANES) 426

3. Experimental Techniques 4314. XANES Spectroscopy and Microspectroscopy at the Carbon

K-Edge 4335. Sulfur-Crosslinks in Rubber 4386. Catalyst for Hydrocarbon Synthesis and Catalytic Reactions 4447. Acknowledgement 4518. References 451

Index 455

ANALYTICALADVANCES FORHYDROCARBON

RESEARCH