Chromatography in the petroleum industry

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Petroleum mixtures consist primarily of relatively unreactive complex hydrocarbons covering a wide boiling range. Such mixtures are difficult to separate by most analytical techniques. Therefore, the petroleum industry has for many years played a leading role in the development of chromatographic methods of analysis. Since the last book specifically concerned with chromatographic analysis of petroleum appeared 15 years ago, numerous advances have been made including developments in liquid and supercritical fluid chromatography, ...

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JOURNAL OF CHROMATOGRAPHY LIBRARY- volume 56 chromatography in the petroleum industry
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JOURNAL OF CHROMATOGRAPHY LIBRARY-volume 56 chromatography in the petroleum industry edited b y E.R. Adlard Burton, South Wirral, UK ELSEVIER Amsterdam-Lausanne-New York-Oxford-Shannon -Tokyo 1995
ELSEVIER SCIENCE B.V. Sara Burgerhartstraat 25 P.O. Box 21 1,1000AE Amsterdam, The Netherlands Library of Congress Cataloging-in-Publication Data Chromatography in the petroleum industry / edited b y E.R. Adlard. p. cm. -- (Journal of chromatography library ; v. 56) Includes bibliographical references and index. ISBN 0-444-89776-3 (acid-free) 1. Petroleum-Analysis. 2. Chromatographic analysis-Industrial applications. I. Adlard, E.R. 11. Series. TP691.C58 1995 665.5’028’7--dc?O 95-30628 CIP ISBN 0-444-89776-3 01995 Elsevier Science B.V. All rights reserved. No part of this publication may be reproduced, stored i n a retrieval system or transmitted i n any form or by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written permission of the publisher, Elsevier Science B.V., Copyright & Permissions Department, P.O. Box 521,1000 A M Amsterdam, The Netherlands. Special regulations for readers i n the U.S.A. - This publication has been registered with the Copyright Clearance Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about conditions under which photocopies of parts of this publication may be made i n the U.S.A.All other copyright questions, including photocopying outside of the U.S.A., should be referred to the publisher. No responsibility is assumed by the publisher for any injury and/or damage t o persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein. This book is printed on acid-free paper. Printed i n The Netherlands
V Contents Foreword .................................................................................................................... XV List of Contributors..................................................................................................... XVII Chapter 1 . The analysis of hydrocarbon gases .................................................. 1 C.J. Cowper 1.1 Introduction ....................................................................................................... 1 1.2 Natural gas ......................................................................................................... 2 1.2.1 Analytical requirements ...................................................................... 5 1.2.1.1 CV measurement ................................................................ 5 1.2.1.2 Hydrocarbon dewpoint calculation..................................... 8 1.2.2 Analytical procedures.......................................................................... 10 1.2.2.1 Isothermal methods............................................................. 10 1.2.2.2 Two detectors ..................................................................... 16 1.2.2.3 C6+ detail............................................................................ 16 1.2.2.4 Temperature programming................................................. 18 1.2.2.5 Combined systems.............................................................. 19 1.2.2.6 Separation in backflush ...................................................... 19 1.2.2.7 Rapid analysis..................................................................... 21 1.2.3 Quantitative measurement................................................................... 25 1.2.3.1 Comprehensive analysis ..................................................... 25 1.2.3.2 Air contamination............................................................... 25 1.2.3.3 Resolution........................................................................... 26 1.2.3.4 Precision ............................................................................. 26 1.2.4.5 Response function .............................................................. 27 1.3 Refinery gas ....................................................................................................... 28 1.3.1 Analytical requirements ...................................................................... 29 1.3.2 Analytical procedures.......................................................................... 30 1.3.3 Sample handling .................................................................................. 37 1.4 Conclusions ....................................................................................................... 38 1.5 Acknowledgements............................................................................................ 39 1.6 References ......................................................................................................... 40 Chapter 2 .Advances in simulated distillation ................................................... 41 D.J. Abbott 2.1 Introduction....................................................................................................... 41 2.2 Middle distillates and lube oils .......................................................................... 42 2.2.1 Precision.............................................................................................. 42 2.2.2 Capillary columns ............................................................................... 44
VI Contents 2.2.3 Aromatics and heteroatoms ................................................................. 44 2.2.4 Multi-element speciation.,................................................................... 45 2.3 Gasolines and gasoline fractions ....................................................................... 46 2.4 Heavy lube oils and residues ..... ................................................................. 47 2.5 Crude oils ................... .................................................................................. 50 2.6 Process control and other applications .............................................................. 51 2.1. Conclusions ........... ....................................................................... 52 2.8 References ....................................... .................................................... 52 Chapter 3 . The chromatographic analysis of refined and synthetic waxes ..... 55 A . Barker 3.1 Introduction .................................................... ............................... 55 3.2 Gas liquid chromatography ......... ................................................................. 57 3.2.1 Establishing present technology .......................................................... 57 3.2.2 The 1980s revolution .......................................................................... 59 3.2.2.1 Sample introduction ............................................................ 60 3.2.2.2 Detection ............................................................................ 64 3.2.2.3 High temperature GLC columns ......................................... 65 3.2.3 Quantitative gas liquid chromatography separation of waxes ............. 70 3.2.3.1 Carbon number distribution analysis .................................. 75 3.3 Supercritical fluid chromatography of waxes .................................................... 78 3.4 Size exclusion chromatography ......................................................................... 81 3.4. I Early work on the SEC analysis of waxes ........................................... 82 3.4.2 Present day technology ........................................................................ 84 3.5 Conclusions ............................... .................................... 89 3.6 References ............. .................................................... 90 Chapter 4 .Hydrodynamic chromatography of polymers ................................. 95 . J Bos and R Tijssen . 4.1 Introduction ............................... ......................................................... 95 4.2 Microcapillary hydrodynamic chromatography ................................................. 96 4.2.1 The0ry ................................................................................................. 96 4.2.2 Expressing the size of macromolecules ............................................... 99 4.2.3 Instrumentation ................................................................................... 100 4.2.3.1 General aspects ................. ..................................... 100 4.2.3.2 Detection ........ .................................................... 102 4.2.3.3 The column ......................................................................... 103 4.2.4 Applications ........................................................................................ 104 4.3 Capillary hydrodynamic chromatography.......................................................... 111 4.3.1 From hydrodynamic chromatography to tubular pinch ....................... 111 4.3.2 Coiling effects ........... ...................................................... 117 4.3.3 Applications ........................................................................................ 119 4.4 Hydrodynamic chromatography in packed columns .......................................... 120 4.5 Conclusions ............................................................................................ 124 4.6 References ................................. ........................................... 125
Contents VII Chapter 5 . Chromatography in petroleum geochemistry ................................. 127 S.J. Rowland and A.T. Revill 5.1 Introduction ....................................................................................................... 127 5.1.1 Recent reviews .................................................................................... 127 5.2 Kerogen and other petroleum macromolecules ................................................. 128 5.3 Geochemistry of petroleum ............................................................................... 130 5.3.1 LC, TLC and TLC-FID ....................................................................... 131 5.3.2 HPLC .................................................................................................. 132 5.3.3 GC ....................................................................................................... 133 5.3.4 GC-MS ................................................................................................ 135 5.3.5 GC-isotope ratio-MS ........................................................................... 137 5.3.6 LC-MS ................................................................................................ 137 5.3.7 SFC, GPC and SEC............................................................................. 138 5.4 Summary............................................................................................................ 138 5.5 References ......................................................................................................... 139 Chapter 6 .The O-FID and its applications in petroleum product analysis .... 143 A.Sironi and G.R. Verga 6.1 Introduction ....................................................................................................... 143 6.2 Oxygenates as components of motor gasoline ................................................... 144 6.2.1 Determination of oxygenates in unleaded fuels................................... 146 6.3 O-FID analyser .................................................................................................. 147 6.3.1 Cracking reactor .................................................................................. 147 6.3.1.1 Low temperature cracker .................................................... 150 6.3.2 Hydrogenation microreactor ............................................................... 151 6.4 Analytical procedure ......................................................................................... 152 6.4.1 Quantitative analysis ........................................................................... 152 6.4.2 Total oxygen determination................................................................. 154 6.4.2.1 Selectivity for oxygenates and sensitivity........................... 155 6.5 O-FID applications............................................................................................ 156 6.6 Conclusion......................................................................................................... 157 6.7 References ......................................................................................................... 157 Chapter 7 . Microwave plasma detectors ............................................................ 159 . A de Wit and J Beens . 7.1 Introduction....................................................................................................... 159 7.2 Principle of operation of an atomic emission detector (AED) ........................... 160 7.3 Historical development of the plasma detector.................................................. 162 7.4 Description and evaluation of a home-built atomic emission detector .............. 164 7.4.1 Description of the apparatus................................................................ 164 7.4.1.1 Microwave cavities............................................................. 164 7.4.1.2 Microwave power supply ................................................... 166 7.4.1.3 Spectrometer....................................................................... 167 7.4.1.4 Optical system .................................................................... 168 7.4.1.5 Sample introduction system................................................ 169
VllI Contents Plasma start-up .................................................................................... 7.4.2 169 Operating limits of the detector ........................................................... 7.4.3 170 7.4.3.1 Emission line intensity ........................................................ 171 7.4.3.2 Plasma pressure .......... ......................... 172 7.4.3.3 Microwave power ............................................................... 172 7.4.3.4 Quartz tube diameter .......................................................... 173 7.4.3.5 Optical system .................................................................... 173 7.4.3.6 Slit width .............................. .................................... 174 7.4.3.7 Upper limit of detection...................................................... 174 7.4.3.8 Type and amount of scavenger gas ..................................... 176 7.4.3.9 Linear dynamic range of the detector ................................. 177 7.4.3.10 Linear dynamic range for hydrogen.................................... 179 7.4.4 Selectivity............................................................................................ 180 7.4.4.1 Selectivity to H, 0 and N .................................................... 180 7.4.4.2 Selectivity to carbon ........................................................... 181 7.5 Conclusions ....................................................................................................... 184 7.6 Description of the Hewlett Packard 592 1A AED .............................................. 184 7.6.1 Gas chromatograph and transfer line ................................................... 185 7.6.2 Microwave cavity, discharge tube and gas flow system ...................... 187 7.6.3 The photodiode array spectrometer ..................................................... 189 7.6.4 Computerized control and data treatment............................................ 190 7.6.5 Characteristics ..................................................................................... 190 7.7 Typical applications .................. ............................................................... 191 7.7.1 Multi-element SimDist ses .......................................................... 191 7.7.1.1 Multi-element SimDist s o h a r e ......................................... 192 7.7.1.2 Linear dynamic ranges ........................................................ 194 7.7.1.3 Simdist results .................................................................... 195 7.7.2 Determination of chlorine-containing compounds in the ethylene oxide process ....................................................................................... 197 7.7.3 Determination of oxygenates in gasoline ............................................ 197 7.7.4 Determination of noble gases in natural gas ........................................ 197 7.7.5 Determination of metal porphyrins in crude oils ................................. 197 7.5 Conclusion................. .................................................... 197 7.9 References ........................................................................... 200 Chapter 8. The sulfur chemiluminescence detector........................................... 201 R.S. Hutte 8.1 Introduction ....................................................................................................... 201 8.2 Sulfur-selective detectors for gas chromatography............................................ 202 8.3 The sulfur chemiluminescence detector ............................................................. 203 8.4 Performance characteristics of the SCD ............................................................ 207 8.5 Factors influencing the sensitivity and selectivity of the SCD ........................... 209 8.6 Flameless sulfur chemiluminescence................................................................. 211 8.7 Column selection and sampling techniques ....................................................... 213 8.8 ADdications ...................................................................................................... 215
Contents IX Refinery gases ..................................................................................... 8.8.1 215 8.8.1.2 Gasoline.............................................................................. 218 8.8.1.3 Diesel fuels ......................................................................... 218 8.8.1.4 High temperature gas chromatography............................... 218 8.9 Conclusions ....................................................................................................... 227 8.10 Acknowledgments ............................................................................................. 227 8.11 References ......................................................................................................... 227 Chapter 9. Multi-column systems in gas chromatography ............................... 231 . H.Mahler. T Maurer and F.Mueller 9.1 Introduction ....................................................................................................... 231 9.1.1 Limitations of single-column systems ................................................. 231 9.1.2 Multi-column systems ......................................................................... 232 9.1.3 Multi-column chromatography............................................................ 233 9.1.3.1 Definition............................................................................ 233 9.1.3.2 Variants of column switching ............................................. 234 9.2 Selectivity tuning in series-coupled columns..................................................... 238 9.3 Column switching techniques ............................................................................ 241 9.3.1 General................................................................................................ 241 9.3.2 Backflushing ....................................................................................... 244 9.3.3 cutting ................................................................................................. 245 9.3.4 Distribution cutting ............................................................................. 246 9.3.5 Special switching techniques............................................................... 249 9.3.5.1 Summation of backflushed compounds .............................. 249 9.3.5.2 Stopped flowlstuttering....................................................... 250 9.3.5.3 Recycle chromatography .................................................... 250 9.4 Practical aspects ................................................................................................ 250 9.4.1 Valve switching................................................................................... 251 9.4.2 Valveless flow switching..................................................................... 252 9.4.2.1 Deans-switching ................................................................. 253 9.4.2.2 Live-switching.................................................................... 255 9.4.3 Column-switching as a sampling technique......................................... 258 9.4.3.1 Sampling fiom a capillary pre-column to a main capillary column ................................................................................ 260 9.4.3.2 Coupling of columns of different type with intermediate trapping............................................................................... 262 9.5 Strategies for the application of multi-column systems ..................................... 263 9.5.1 General remarks .................................................................................. 263 9.5.2 Guidelines for the use of single- or multi-column systems.................. 266 9.6 References ......................................................................................................... 266 Chapter 10 . Supercritical fluid extraction ........................................................... 269 T.P. Lynch 10.1 Introduction ....................................................................................................... 269 10.2 Why use supercritical fluid extraction? ............................................................. 271
x Contents 10.2.1 Technical advantages .. .................................................. 27 1 10.2.1. 1 Solubility ........................ ........................................... 271 10.2.1.2 Selectivity ........................................................................... 271 10.2.1.3 Volatility ............................................................................. 274 10.2.1.4 Matrix penetration .............................................................. 274 10.2.2 Environmental and safety advantages ................................................. 275 10.3 ................................................................ 275 ms ................................................................................. 276 10.3.2 Sample vessels and temperature control .............................................. 277 10.3.3 Depressurization .............................. 278 10.3.4 Extract collection ................................................................................ 278 10.4 SFE techniques ............... ............................................... 280 10.4.1 Static extraction . .................................................... 280 10.42 Dynamic extract ............................................... 280 10.4.3 Recirculating extraction ...................................................................... 281 10.4.4 Extraction of liquids .. ........................................ 281 10.4.5 Reactive extraction .... ........................................ 283 10.4.6 Off-line extraction ............................................................................... 283 10.4.7 On-line extraction...... ........................................ 284 10.5 Petroleum-based applications ...... ............................................................. 284 10.5.1 Off-line applications ............................................................................ 284 10.5.1.1 Residual oil on drill cuttings ............................................... 284 10.5.1.2 Drilling mud characterization ............................................. 286 10.5.1.3 Petroleum core and rock extractions................................... 287 10.5.1.4 Refinery catalysts, deposits and sludges ............................. 288 10.5.1.5 Automotive engine particulates .......................................... 288 10.5.1.6 Environmental analysis ....................................................... 290 10.5.2 On-line applications ............................................................................ 291 10.5.2.1 On-line SFE-GC ................................................................. 291 10.5.2.2 On-line SFE-HPLC............................................................. 299 10.6 Conclusion ......................................................................................................... 301 10.7 References .. .............. ............................... 301 Chapter 11. Supercritical fluid chromatography ................................................ 305 . 1 Roberts 1 1 . 1 Introduction ..... ................................................................... 305 1 1.2 Instrumentation .................................................................................................. 306 1 I .2.1 Mobile phase pumps ........................................................................... 307 1 1.2.I . 1 Reciprocating pumps ........ ...................................... 308 1 1.2.1.2 Syringe pumps .................................................................... 308 I 1.2.2 Ovendtemperature control ................ ...................................... 309 11.2.3 Injectors .............................................................................................. 309 1 1.2.4 Detectors . ................................................................ 310 11.2.4.1 Universal detectors ............................................................. 311 1 1.2.4.2 Spectroscopic detectors ...................................................... 314
Contents XI 11.2.4.3 Element specific detection.................................................. 318 11.2.5 Restrictors ........................................................................................... 320 11.2.5.1 Fixed restrictors.................................................................. 320 11.2.5.2 Variable restrictors ............................................................. 321 1 1.3 Applications ...................................................................................................... 322 11.3.1 Simulated distillation........................................................................... 322 11.3.2 Hydrocarbon group type analysis........................................................ 328 11.3.2.1 Gasolines ............................................................................ 330 11.3.2.2 Kerosenes and naphthas...................................................... 334 11.3.2.3 Diesel fuels ......................................................................... 336 11.4 References ......................................................................................................... 343 Chapter 12 . HPLC and column liquid chromatography .................................... 347 A.C. Neal 12.1 Introduction....................................................................................................... 347 12.2 Apparatus .......................................................................................................... 348 12.2.1 Solvent reservoirs ................................................................................ 348 12.2.2 Pumps.................................................................................................. 348 12.2.3 Sample injectors.................................................................................. 350 12.2.4 Columns .............................................................................................. 351 12.2.5 Detectors ............................................................................................. 353 12.2.6 Selective property detectors ................................................................ 353 12.2.6.1 UV-visible spectrophotometers .......................................... 353 12.2.6.2 Diode array detectors (DAD) ............................................. 354 12.2.6.3 Fluorescence detectors........................................................ 355 12.2.6.4 Electrochemical detectors................................................... 355 12.2.6.5 Flame ionization detector ................................................... 356 12.2.6.6 Mass spectrometers ............................................................ 356 12.2.6.7 Infrared and NMR .............................................................. 357 12.2.7 Bulk property detectors....................................................................... 358 12.2.7.1 Refractive index detector.................................................... 358 12.2.7.2 Evaporative light scattering detectors................................. 359 12.2.7.3 Dielectric constant detector ................................................ 360 12.3 Quantitation....................................................................................................... 361 12.4 Applications ...................................................................................................... 362 12.4.1 Individual compounds ......................................................................... 362 12.4.1.1 Polycyclic aromatic hydrocarbons (PAHs)......................... 362 12.4.1.2 Other indigenous compounds ............................................. 365 12.4.1.3 Additives and contaminants................................................ 366 12.4.1.4 Compound classes .............................................................. 368 12.5 Preparative HPLC and column liquid chromatography..................................... 370 12.5.1 Standard methods ................................................................................ 370 12.6 Individual publications ...................................................................................... 371 12.7 Future trends...................................................................................................... 372 12.8 References ......................................................................................................... 372
XI1 Contents Chapter 13. Modern data handling methods ....................................................... 375 N. Dyson 1 3.1 Introduction ............................... ...................................... 375 13.2 The role ofthe data processor ........................................................................... 376 13.2.1 The modem integrator has four distinct roles ..... .......................... 376 13.2.2 Lab economics .................................................................................... 378 13.2.3 Prepare and distribute data, information and reports ........................... 378 13.3 Limitations of the detector signal ......... .................................................. 378 13.3.1 Injector fractionation is uniform .................... ............................. 378 13.3.2 All solutes of inte ........................ 379 13.3.3 Column resolution is ........................ 379 13.3.4 All solutes of interest ........................ 379 13.3.5 Signalinoise ratio ........................ 379 13.3.6 Detector is linear ............................. 380 13.4 Detector signal processing .... ........................ 380 13.4.1 Improving signal to ........................ 380 13.4.2 Electronic filtering ............................ .......................... 381 13.4.3 Software smoothing ..... ............................................. 13.4.4 Measurement of pe ........................ 381 13.4.5 Baseline placement ....... ...................................... I 3.4.6 Mathematical separation (deconvolution) of peaks and integrator developments ................................... ...................................... 382 13.4.7 Selective extraction ..... ................................................. 383 13.4.7.1 Peak model1 ...................................... 383 13.4.7.2 Signal subtraction ............................................................... 383 13.4.8 Resolution enhancement. .... .................................................... 384 13.5 Measurement errors .................... 384 13.5.1 Accuracy 13.5.2 Errors crea .......................... 385 13.5.3 Errors crea 13.5.4 Errors created by asymmetry ...................... .................... 386 13.5.5 Transmission of systematic errors through oups ............. 387 13.5.6 Baseline construction errors ................................................................ 390 13.5.7 Errors of tangent/perpendicular peak splitting .................................... 390 33.5.8 Ease of use ............................... ................................................ 390 13.6 Calibration ......... ................................................ 390 13.6.1 Use of area or height for quantitation .................................................. 390 13.6.2 Calculations and response factors ........................................ 13.6.3 Limitations of the standard calculations .............................................. 391 ................................................. 391 ................................................. 392 13.6.3.3 External standard ................................................ 13.6.4 Calibration curves ............................. .......................................... 392 13.6.5 Empirical correction of analysis errors ................................................ 393 13.7 Validation and standard chromatograms ........................................................... 393
Contents X1 I1 13.7.1 Meaning of validation ......................................................................... 393 13.7.2 System suitability................................................................................ 394 13.7.3 Validation and standard chromatograms............................................. 394 13.8 Strategies for peak measurement ....................................................................... 395 13.8.1 Noise ................................................................................................... 396 13.8.2 Baseline drift ....................................................................................... 396 13.8.3 Peak overlap........................................................................................ 396 13.8.4 Asymmetry .......................................................................................... 396 13.8.5 Detectors ............................................................................................. 397 133.6 Integrators ........................................................................................... 397 13.8.7 Checking the analysis results ............................................................... 397 13.8.7.1 Checking the chromatogram............................................... 397 133.7.2 Checking the analysis rep0rt ............................................... 398 13X7.3 Accepting the results .......................................................... 398 13.9 References ......................................................................................................... 398 Chapter 14 . Capillary electrophoresis in the petroleum industry ...................... 401 . T Jones and G Bondoux . 14.1 Introduction ....................................................................................................... 401 14.2 Separation techniques ........................................................................................ 404 14.2.1 Free-zone capillary electrophoresis(FZCE) ....................................... 404 14.2.2 Micellar electrokinetic chromatography (MEKC)............................... 408 14.2.3 Gel filled capillary electrophoresis(GFCE)........................................ 411 14.2.4 Capillary isoelectric focusing (CIEF).................................................. 412 14.2.5 Instrumentation ................................................................................... 412 14.2.6 Capillary.............................................................................................. 412 14.2.7 High voltage power supply.................................................................. 413 14.2.8 Temperature control ............................................................................ 413 14.2.9 Injection .............................................................................................. 414 14.2.10 Detection ............................................................................................. 415 14.2.10.1 UV detection ...................................................................... 416 14.2.10.2 Fluorescence, indirect fluorescence, laser-induced fluo- rescence .............................................................................. 418 14.2.10.3 Amperometric detection, conductometric detection, MS detection ............................................................................. 419 14.3 Applications of capillary electrophoresis.......................................................... 421 14.4 Conclusion......................................................................................................... 424 14.5 References ......................................................................................................... 425 Subject Index ............................................................................................................ 427
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XV Foreword Although the spectacular development of gas chromatography in the 1950s and 1960s is now a fading memory of a golden era, there are still advances being made in apparatus, technique and applications. The petroleum industry makes use of all the variants of chromatography as should be clear from the present volume, but gas chromatography in particular is the most important analytical technique in petroleum analysis and has been since its first announcement by James and Martin in 1952. Indeed it is no exaggeration to claim that many of the major advances in gas chromatography in that golden era emanated from the laboratories of the petroleum industry. This book is intended primarily for those concerned with the analysis of crude oil and its products but many of the chapters have much broader applications. It is hoped, therefore, that many outside the immediate sphere of petroleum analy- sis will find sufficient of interest to make it a worthwhile purchase. In multi-author books there will be inevitable variations in the style and con- tent of each contribution. There is no reason why this should be regarded as a weakness since as William Cowper pointed out “variety’s the very spice of life”. Likewise a small amount of overlap between some chapters is not a drawback if it allows each chapter to be a freestanding account of a particular topic. It was interesting to reread the comments of the editors of the only other book dedicated to the subject of petroleum analysis by chromatography published 15 years ago. These editors spent some time describing the reasons for the choice of the title of their book. In this context, it is interesting that the original title intended for their book was the one used here. In concluding this foreword, I should like to thank all the contributors and El- sevier for their efforts to make this both a useful and an interesting volume. E.R.Adlard
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XVII List of Contributors D.J. ABBOTT Esso Research Centre, Analytical Group, Abingdon, Oxford- shire OX13 6AE, UK A. BARKER Dussek Campbell Ltd, Thames Road, Crayford, Dartford, Kent DAI 4Q.J UK J. BEENS Koninklijke/ShelI-Laboratorium, Amsterdam {Shell Research B. K), Badhuisweg 3, 1031 CMAmsterdam, The Netherlands G. BONDOUX Waters Chromatography Division, Millipore S.A., 6 Rue Jean- Pierre Timbaud, BP 307, 78054 St. Quentin-en- yvelines, France J. BOS Koninkl~~/SheII-Laboratorium, Amsterdam {Shell Research B. K), Badhuisweg 3, 1031 CMAmsterdam, The Netherlands C.J. COWER 84, West Grove, Walton on Thames, Surrey KT12 5PD, UK A. DE WIT KoninklijkdShell-Laboratorium, Amsterdam (Shell Research B. K), Badhuisweg 3, 1031 CMAmsterdam, The Netherlands N. DYSON @son Instruments Ltd, Hatton Lyons Industrial Estate, Hatton, Houghton-le-Spring, Tyne and Wear DH5 O ,m UK R.S. HUTTE Sievers Instruments Inc., 1930 Central Avenue, Suite C, Boul- der, CO 80301, USA T. JONES Waters Chromatography Division, MiIlipore (CK) Ltd, Winster House, Heronsway, Chester Business Park, Wrexham Road, Chester CH4 SQR, UK T.P. LYNCH Analytical & Applied Science Division, BP Research & Engi- neering Centre, Sunbury-on-Thames, Middlesex, T W I 6 7LN UK H. MAHLER Siemens AG, Abt AUT 35 CHR, Postfach 21 12 62, 76187 Karlsruhe, Germany T. MAURER Siemens AG, Abt AUT 35 CHR, Postfach 21 12 62, 76187 Karlsruhe, Germany F. MUELLER Siemens AG, Abt AUT 35 CHR, Postfach 21 12 62, 76187 Karlsruhe, Germany A.C. NEAL Esso Research Centre, Milton Hill, Abingdon, Oxfordshire OX13 6AE. UK
XVIII List o contributors f 1. ROBERTS Analytical & Applied Science Division, BP Research & Engi- neering Centre, Sunbury-on-Thames, Middlesex, TW16 7LN, UK A.T. REVILL CSIRO Division of Oceanography, Castray Esplanade, Hobart, Tasmania, Australia S.J. ROWLAND Petroleum and Environmental Geochemistry Group, Depart- ment of Environmental Sciences, Universily of Plymouth, Drake Circus, Plymouth, PL4 8AA, UK A. SIRONI Fisons Instruments, Strada Rivoltana, 20090 Rodano (Milan), Italy R. TIJSSEN KoninklijkdShell-Laboratorium, Amsterdam (Shell Research B. V.), Badhuisweg 3, I03 I CM Amsterdam, The Netherlands G.R. VERGA Fisons instruments, Strada Rivoltana, 20090 Rodano (Milan), Italy
E.R. Adlard (Ed.), Chromatography i the Petroleum Industry n Journal of Chromatography Library Series, Vol. 56 0 1995 Elsevier Science B.V. All rights reserved 1 CHAPTER 1 The analysis o hydrocarbon gases f C.J. Cowper” British Gaspfc,London Research Station, Michael Road, London SW6 ZAD, UK “That man ... sat down to write a book, to tell the world what the world had all his life been telling him.” Boswell’s Life of Johnson 1.1 INTRODUCTION Hydrocarbon gases can be categorized in a number of ways, one of which is to define them as natural or man-made. Natural gas is a major energy source for domestic, commercial and industrial consumers, and is used, so far as possible, with minimum change to the compo- sition found in the reservoir. It consists generally of methane and other saturated hydrocarbons and some non-flammable gases. Man-made gases arise from refin- ing operations on liquid hydrocarbon feedstocks, and their compositions vary widely according to the process from which they are derived. Those components found in natural gas are likely to be present, in addition to unsaturated hydrocar- bons. Gas chromatography is the principal analytical method used for hydrocarbon gases. Particular components can be measured by spectroscopic or chemical means, but for analysis of the bulk of components, the separating power of chromatography is both essential and well developed. Although gases are often considered to be simple mixtures, their analysis has frequently tested the ability of gas chromatography, either because of the range of components present (boiling range, or concentration spread, or both), or be- cause of the need to use highly specific stationary phases to separate apparently intractable pairs of components. The different separating requirements relating to groups of components within the same gas mixture has led to the use of multi- column systems, with columns being isolated or reversed, or their order changed * Current address: 84, West Grove, Walton on Thames, Surrey KT12 SPD, UK. References p . 40