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JOURNAL OF CHROMATOGRAPHY LIBRARY- volume 56
chromatography in the
petroleum industry
This Page Intentionally Left Blank
JOURNAL OF CHROMATOGRAPHY LIBRARY-volume 56
chromatography in the
petroleum industry
edited by
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 by 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
0 1995 Elsevier Science B.V. All rights reserved.
No part of this publication may be reproduced, stored in a retrieval system or transmitted in 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 AM Amsterdam, The Netherlands.
Special regulations for readers in 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 in
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 to 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 in The Netherlands
V
Contents
Foreword .................................................................................................................... XV
List of Contributors ..................................................................................................... XVII
Chapter 1 . The analysis of hydrocarbon gases .................................................. C.J. Cowper
1.1 Introduction ....................................................................................................... 1.2 Natural gas ......................................................................................................... 1.2.1 Analytical requirements ......................................................................
1.2.1.2 Hydrocarbon dewpoint calculation ..................................... 1.2.2 Analytical procedures ..........................................................................
1.2.2.3 C6+ detail ............................................................................ 1.2.2.4 Temperature programming .................................................
1.2.2.6 Separation in backflush ......................................................
1.2.3 Quantitative measurement ...................................................................
1.2.1.1 CV measurement ................................................................
1.2.2.1 Isothermal methods ............................................................. 1.2.2.2 Two detectors .....................................................................
1.2.2.5 Combined systems ..............................................................
1.2.2.7 Rapid analysis .....................................................................
1.2.3.1 Comprehensive analysis ..................................................... 1.2.3.2 Air contamination ............................................................... 1.2.3.3 Resolution ........................................................................... 1.2.3.4 Precision ............................................................................. 1.2.4.5 Response function .............................................................. 1.3 Refinery gas ....................................................................................................... 1.3.1 Analytical requirements ...................................................................... 1.3.2 Analytical procedures .......................................................................... 1.3.3 Sample handling .................................................................................. 1.4 Conclusions ....................................................................................................... 1.5 Acknowledgements ............................................................................................ 1.6 References .........................................................................................................
1
1
2
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5
8
10
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16
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25
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25
26
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30
37
38
39
40
Chapter 2 . Advances in simulated distillation ................................................... 41
2.1 Introduction ....................................................................................................... 41
2.2 Middle distillates and lube oils .......................................................................... 42
2.2.1 Precision .............................................................................................. 42
D.J. Abbott
2.2.2 Capillary columns ............................................................................... 44
VI Contents
2.2.3 Aromatics and heteroatoms .................................................................
2.2.4 Multi-element speciation., ...................................................................
2.3 Gasolines and gasoline fractions .......................................................................
2.4 Heavy lube oils and residues ..... .................................................................
2.5 Crude oils ................... ..................................................................................
2.6 Process control and other applications .............................................................. 2.1. Conclusions .......................................................................
2.8 References ....................................... .................................................... ...........
Chapter 3 . The chromatographic analysis of refined and synthetic waxes .....
3.1
3.2
3.3
3.4
3.5
3.6
A . Barker
Introduction .................................................... ...............................
Gas liquid chromatography ......... ................................................................. 3.2.1 Establishing present technology .......................................................... 3.2.2 The 1980s revolution ..........................................................................
3.2.2.1 Sample introduction ............................................................
3.2.2.2 Detection ............................................................................
3.2.2.3 High temperature GLC columns ......................................... Quantitative gas liquid chromatography separation of waxes .............
3.2.3.1
3.2.3
Carbon number distribution analysis .................................. Supercritical fluid chromatography of waxes ....................................................
Size exclusion chromatography .........................................................................
3.4. I Early work on the SEC analysis of waxes ........................................... 3.4.2 Present day technology ........................................................................ Conclusions ............................... ....................................
References ............. ....................................................
Chapter 4 .
4.1 Introduction ............................... .........................................................
4.2 Microcapillary hydrodynamic chromatography ................................................. 4.2.1 The0 ry .................................................................................................
4.2.2 Expressing the size of macromolecules ............................................... 4.2.3 Instrumentation ...................................................................................
4.2.3.1 General aspects ................. ..................................... 4.2.3.2 Detection ........ ....................................................
4.2.3.3 The column .........................................................................
4.2.4 Applications ........................................................................................
4.3.1 From hydrodynamic chromatography to tubular pinch ....................... 4.3.2 Coiling effects ........... ......................................................
4.3.3 Applications ........................................................................................
4.4
4.5 Conclusions ............................................................................................
4.6 References ................................. ...........................................
Hydrodynamic chromatography of polymers .................................
J . Bos and R . Tijssen
4.3 Capillary hydrodynamic chromatography ..........................................................
Hydrodynamic chromatography in packed columns ..........................................
44
45
46
47
50
51
52
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57
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59
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64
65
70
75
78
81
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89
90
95
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96
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102
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104
111
111
117
119
120
124
125
Contents VII
Chapter 5 . Chromatography in petroleum geochemistry ................................. 127
S.J. Rowland and A.T. Revill
5.1
5.2
5.3
5.4
5.5
Introduction ....................................................................................................... 5.1.1 Recent reviews .................................................................................... Kerogen and other petroleum macromolecules ................................................. Geochemistry of petroleum ............................................................................... 5.3.1 LC, TLC and TLC-FID ....................................................................... 5.3.2 HPLC .................................................................................................. 5.3.3 GC ....................................................................................................... 5.3.4 GC-MS ................................................................................................
5.3.6 LC-MS ................................................................................................ 5.3.5 GC-isotope ratio-MS ...........................................................................
5.3.7 SFC, GPC and SEC ............................................................................. Summary ............................................................................................................
References .........................................................................................................
Chapter 6 . The O-FID and its applications in petroleum product analysis ....
Oxygenates as components of motor gasoline ................................................... Determination of oxygenates in unleaded fuels ...................................
6.3.1 Cracking reactor ..................................................................................
6.3.2 Hydrogenation microreactor ............................................................... 6.4 Analytical procedure ......................................................................................... 6.4.1 Quantitative analysis ........................................................................... 6.4.2 Total oxygen determination ................................................................. Selectivity for oxygenates and sensitivity ........................... 6.5 O-FID applications ............................................................................................
A . Sironi and G.R. Verga
6.1 Introduction .......................................................................................................
6.2
6.3 O-FID analyser ..................................................................................................
6.3.1.1 Low temperature cracker ....................................................
6.2.1
6.4.2.1
6.6 Conclusion ......................................................................................................... 6.7 References .........................................................................................................
Chapter 7 . Microwave plasma detectors ............................................................
Principle of operation of an atomic emission detector (AED) ........................... Historical development of the plasma detector .................................................. Description and evaluation of a home-built atomic emission detector ..............
A . de Wit and J . Beens
7.1 Introduction ....................................................................................................... 7.2
7.3
7.4
7.4.1 Description of the apparatus ................................................................ 7.4.1.1 Microwave cavities ............................................................. 7.4.1.2 Microwave power supply ................................................... 7.4.1.3 Spectrometer .......................................................................
7.4.1.5 Sample introduction system ................................................
7.4.1.4 Optical system ....................................................................
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127
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150
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169
VllI Contents
7.4.2 Plasma start-up ....................................................................................
7.4.3 Operating limits of the detector ...........................................................
7.4.3.1 Emission line intensity ........................................................ 7.4.3.2 Plasma pressure .......... .........................
7.4.3.3 Microwave power ...............................................................
7.4.3.4 Quartz tube diameter ..........................................................
7.4.3.5 Optical system ....................................................................
7.4.3.6 Slit width .............................. ....................................
7.4.3.7 Upper limit of detection ......................................................
7.4.3.8 Type and amount of scavenger gas ..................................... 7.4.3.9 Linear dynamic range of the detector .................................
7.4.3.10 Linear dynamic range for hydrogen .................................... 7.4.4 Selectivity ............................................................................................ 7.4.4.1 Selectivity to H, 0 and N .................................................... 7.4.4.2 Selectivity to carbon ........................................................... 7.5 Conclusions .......................................................................................................
7.6 Description of the Hewlett Packard 592 1 A AED ..............................................
7.6.1 Gas chromatograph and transfer line ................................................... 7.6.2 Microwave cavity, discharge tube and gas flow system ...................... 7.6.3 The photodiode array spectrometer .....................................................
7.6.4 Computerized control and data treatment ............................................ 7.6.5 Characteristics .....................................................................................
7.7 Typical applications .................. ............................................................... 7.7.1 Multi-element SimDist ses .......................................................... 7.7.1.1 Multi-element SimDist sohare ......................................... 7.7.1.2 Linear dynamic ranges ........................................................ 7.7.1.3 Simdist results ....................................................................
Determination of chlorine-containing compounds in the ethylene
oxide process .......................................................................................
Determination of oxygenates in gasoline ............................................
Determination of metal porphyrins in crude oils .................................
7.7.2
7.7.3
7.7.4
7.7.5
Determination of noble gases in natural gas ........................................
7.5 Conclusion ................. .................................................... 7.9 References ...........................................................................
Chapter 8 . The sulfur chemiluminescence detector ........................................... R.S. Hutte
8.1 Introduction .......................................................................................................
8.2 Sulfur-selective detectors for gas chromatography ............................................
8.3 The sulfur chemiluminescence detector .............................................................
8.4 Performance characteristics of the SCD ............................................................ 8.5 Factors influencing the sensitivity and selectivity of the SCD ...........................
8.6 Flameless sulfur chemiluminescence .................................................................
8.7 Column selection and sampling techniques ....................................................... 8.8 ADdications ......................................................................................................
169
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202
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209
211
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215
Contents IX
8.8.1 Refinery gases ..................................................................................... 8.8.1.2 Gasoline .............................................................................. 8.8.1.3 Diesel fuels ......................................................................... 8.8.1.4 High temperature gas chromatography ...............................
8.9 Conclusions ....................................................................................................... 8.10 Acknowledgments ............................................................................................. 8.11 References .........................................................................................................
Chapter 9 . Multi-column systems in gas chromatography ............................... H . Mahler. T . Maurer and F . Mueller
9.1 Introduction ....................................................................................................... 9.1.1 Limitations of single-column systems ................................................. 9.1.2 Multi-column systems ......................................................................... 9.1.3 Multi-column chromatography ............................................................ 9.1.3.1 Definition ............................................................................
9.1.3.2 Variants of column switching ............................................. 9.2 Selectivity tuning in series-coupled columns ..................................................... 9.3 Column switching techniques ............................................................................ 9.3.1 General ................................................................................................ 9.3.2 Backflushing ....................................................................................... 9.3.3 cutting ................................................................................................. 9.3.4 Distribution cutting ............................................................................. 9.3.5 Special switching techniques ............................................................... Summation of backflushed compounds .............................. 9.3.5.2 Stopped flowlstuttering ....................................................... 9.3.5.3 Recycle chromatography ....................................................
9.3.5.1
9.4 Practical aspects ................................................................................................ 9.4.1 Valve switching ................................................................................... 9.4.2 Valveless flow switching .....................................................................
9.4.2.2 Live-switching .................................................................... Column-switching as a sampling technique ......................................... 9.4.3.1 Sampling fiom a capillary pre-column to a main capillary
column ................................................................................
9.4.3.2 Coupling of columns of different type with intermediate
9.4.2.1 Deans-switching .................................................................
9.4.3
trapping ............................................................................... Strategies for the application of multi-column systems ..................................... 9.5.1 General remarks .................................................................................. 9.5.2 Guidelines for the use of single- or multi-column systems .................. 9.6 References .........................................................................................................
9.5
Chapter 10 . Supercritical fluid extraction ........................................................... T.P. Lynch
10.1 Introduction ....................................................................................................... 10.2 Why use supercritical fluid extraction? .............................................................
215
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x
10.3
10.4
10.5
10.6
10.7
Contents
10.2.1 Technical advantages .. ..................................................
10.2.1.2 Selectivity ...........................................................................
10.2.1.3 Volatility .............................................................................
10.2.1.4 Matrix penetration ..............................................................
Environmental and safety advantages .................................................
ms .................................................................................
10.3.2 Sample vessels and temperature control ..............................................
10.3.4 Extract collection ................................................................................
SFE techniques ............... ...............................................
10.4.1 Static extraction . ....................................................
10.42 Dynamic extract ...............................................
10.4.3 Recirculating extraction ......................................................................
10.4.4 Extraction of liquids .. ........................................
10.4.5 Reactive extraction .... ........................................
10.4.6 Off-line extraction ...............................................................................
10.4.7 On-line extraction ...... ........................................
Petroleum-based applications ...... .............................................................
10.5.1 Off-line applications ............................................................................ 10.5.1.1 Residual oil on drill cuttings ............................................... 10.5.1.2 Drilling mud characterization .............................................
10.5.1.3 Petroleum core and rock extractions ...................................
10.5.1.4 Refinery catalysts, deposits and sludges .............................
10.5.1.5 Automotive engine particulates ..........................................
10.5.1.6 Environmental analysis .......................................................
10.5.2 On-line applications ............................................................................
10.5.2.1 On-line SFE-GC .................................................................
10.5.2.2 On-line SFE-HPLC .............................................................
Conclusion .........................................................................................................
References .. .............. ...............................
10.2.1 . 1 Solubility ........................ ...........................................
10.2.2
................................................................
10.3.3 Depressurization ..............................
27 1
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299
301
301
Chapter 11 . Supercritical fluid chromatography ................................................ 1 . Roberts
1 1.1 Introduction ..... ................................................................... 1 1.2 Instrumentation ..................................................................................................
Mobile phase pumps ...........................................................................
1 1.2.1.2 Syringe pumps ....................................................................
I 1.2.2 Ovendtemperature control ................ ......................................
11.2.3 Injectors ..............................................................................................
1 1.2.4 Detectors . ................................................................ 11.2.4.1 Universal detectors .............................................................
1 1.2.4.2 Spectroscopic detectors ......................................................
1 I . 2.1
1 1.2. I . 1 Reciprocating pumps ........ ......................................
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307
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308
309
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314
Contents XI
11.2.4.3 Element specific detection .................................................. 1 1.2.5 Restrictors ........................................................................................... 11.2.5.1 Fixed restrictors ..................................................................
11.2.5.2 Variable restrictors ............................................................. 1 1.3 Applications ......................................................................................................
11.3.1 Simulated distillation ...........................................................................
1 1.3.2 Hydrocarbon group type analysis ........................................................ 1 1.3.2.1 Gasolines ............................................................................ 11.3.2.2 Kerosenes and naphthas ...................................................... 11.3.2.3 Diesel fuels ......................................................................... 11.4 References .........................................................................................................
Chapter 12 . HPLC and column liquid chromatography ....................................
A.C. Neal
12.1 Introduction .......................................................................................................
12.2 Apparatus .......................................................................................................... 12.2.1 Solvent reservoirs ................................................................................ 12.2.2 Pumps .................................................................................................. 12.2.3 Sample injectors .................................................................................. 12.2.4 Columns .............................................................................................. 12.2.5 Detectors ............................................................................................. 12.2.6 Selective property detectors ................................................................ 12.2.6.1 UV-visible spectrophotometers .......................................... 12.2.6.2 Diode array detectors (DAD) ............................................. 12.2.6.3 Fluorescence detectors ........................................................ 12.2.6.4 Electrochemical detectors ................................................... 12.2.6.5 Flame ionization detector ................................................... 12.2.6.6 Mass spectrometers ............................................................ 12.2.6.7 Infrared and NMR .............................................................. 12.2.7 Bulk property detectors ....................................................................... 12.2.7.1 Refractive index detector .................................................... 12.2.7.2 Evaporative light scattering detectors ................................. 12.2.7.3 Dielectric constant detector ................................................
12.4 Applications ......................................................................................................
12.4.1.1 Polycyclic aromatic hydrocarbons (PAHs) ......................... 12.4.1.2 Other indigenous compounds ............................................. 12.4.1.3 Additives and contaminants ................................................ 12.4.1.4 Compound classes ..............................................................
12.5 Preparative HPLC and column liquid chromatography ..................................... 12.5.1 Standard methods ................................................................................
12.7 Future trends ...................................................................................................... 12.8 References .........................................................................................................
12.3 Quantitation .......................................................................................................
12.4.1 Individual compounds .........................................................................
12.6 Individual publications ......................................................................................
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3 72
XI1 Contents
Chapter 13. Modern data handling methods ....................................................... 375
The role ofthe data processor ...........................................................................
13.2.1 The modem integrator has four distinct roles ..... .......................... 376
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
N. Dyson
1 3.1 Introduction ............................... ...................................... 375
13.2 376
13.2.2 Lab economics .................................................................................... 378
13.4.3 Software smoothing ..... ............................................. 13.4.4 Measurement of pe ........................ 381
13.4.5 Baseline placement ....... ......................................
developments ................................... ...................................... 382
13.4.7 Selective extraction ..... ................................................. 383
13.4.7.2 Signal subtraction ............................................................... 383
13.4.8 Resolution enhancement. .... .................................................... 384
13.5.2 Errors crea .......................... 385
13.5.4 Errors created by asymmetry ...................... .................... 386
13.5.5 Transmission of systematic errors through oups ............. 387
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
I 3.4.6 Mathematical separation (deconvolution) of peaks and integrator
13.4.7.1 Peak model1 ...................................... 383
13.5 Measurement errors .................... 384
13.5.1 Accuracy
13.5.3 Errors crea
13.5.6 Baseline construction errors ................................................................ 390
13.6.2
13.6.3 Limitations of the standard calculations .............................................. 391
................................................. 391
................................................. 392
13.6.4 Calibration curves ............................. .......................................... 392
Calculations and response factors ........................................
1 3.6.3.3 External standard ................................................
13.6.5 Empirical correction of analysis errors ................................................ 393
13.7 Validation and standard chromatograms ........................................................... 393
Contents XI11
13.7.1 Meaning of validation ......................................................................... 13.7.2 System suitability ................................................................................ 13.7.3 Validation and standard chromatograms ............................................. Strategies for peak measurement .......................................................................
13.8.1 Noise ................................................................................................... 13.8.2 Baseline drift ....................................................................................... 13.8.3 Peak overlap ........................................................................................ 13.8.4 Asymmetry ..........................................................................................
13 3.6 Integrators ........................................................................................... Checking the analysis results ............................................................... 13.8.7.1 Checking the chromatogram ............................................... Checking the analysis rep0 rt ............................................... Accepting the results ..........................................................
13.8
13.8.5 Detectors .............................................................................................
13.8.7
13 3.7.2
13 X7.3
13.9 References .........................................................................................................
Chapter 14 . Capillary electrophoresis in the petroleum industry ...................... T . Jones and G . Bondoux
14.1 Introduction ....................................................................................................... 14.2 Separation techniques ........................................................................................ 14.2.1 Free-zone capillary electrophoresis (FZCE) ....................................... 14.2.2 Micellar electrokinetic chromatography (MEKC) ...............................
14.2.3 Gel filled capillary electrophoresis (GFCE) ........................................ 14.2.4 Capillary isoelectric focusing (CIEF) .................................................. 14.2.5 Instrumentation ................................................................................... 14.2.6 Capillary .............................................................................................. 14.2.7 High voltage power supply ..................................................................
14.2.8 Temperature control ............................................................................ 14.2.9 Injection .............................................................................................. 14.2.10 Detection ............................................................................................. 14.2.10.1 UV detection ...................................................................... 14.2.10.2 Fluorescence, indirect fluorescence, laser-induced fluorescence .............................................................................. 14.2.10.3 Amperometric detection, conductometric detection, MS
detection ............................................................................. 14.3
14.4 Conclusion ......................................................................................................... 14.5 References .........................................................................................................
Applications of capillary electrophoresis ..........................................................
393
394
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395
396
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397
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398
398
398
401
401
404
404
408
411
412
412
412
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414
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416
418
419
421
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Subject Index ............................................................................................................ 427
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