Adlard E.R. (ed.) Chromatography in the Petroleum Industry
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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
271
271
274
274
275
275
276
277
278
278
280
280
280
281
281
283
283
284
284
284
284
286
287
288
288
290
291
291
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
........
......................................
305
305
306
307
308
308
309
309
310
311
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
......................................................................................
318
320
320
321
322
322
328
330
334
336
343
347
347
348
348
348
350
351
353
353
353
354
355
355
356
356
357
358
358
359
360
361
362
362
362
365
366
368
370
370
371
372
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 fluo-
rescence
..............................................................................
14.2.10.3
Amperometric detection, conductometric detection, MS
detection
.............................................................................
14.3
14.4
Conclusion
.........................................................................................................
14.5
References
.........................................................................................................
Applications of capillary electrophoresis
..........................................................
393
394
394
395
396
396
396
396
397
397
397
397
398
398
398
401
401
404
404
408
411
412
412
412
413
413
414
415
416
418
419
421
424
425
Subject Index
............................................................................................................
427
This Page Intentionally Left Blank
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
This Page Intentionally Left Blank
XVII
List
of
Contributors
D.J. ABBOTT
A. BARKER
J.
BEENS
G.
BONDOUX
J.
BOS
C.J.
COWER
A. DE WIT
N.
DYSON
R.S.
HUTTE
T. JONES
T.P. LYNCH
H.
MAHLER
T. MAURER
F.
MUELLER
A.C.
NEAL
Esso Research Centre, Analytical Group, Abingdon, Oxford-
shire
OX1
3 6AE, UK
Dussek Campbell Ltd, Thames Road, Crayford, Dartford, Kent
DAI 4Q.J UK
Koninklijke/ShelI-Laboratorium,
Amsterdam {Shell Research
B.
K),
Badhuisweg 3, 1031 CMAmsterdam, The Netherlands
Waters Chromatography Division, Millipore S.A., 6 Rue Jean-
Pierre Timbaud, BP 307, 78054
St.
Quentin-en- yvelines,
France
Koninkl~~/SheII-Laboratorium,
Amsterdam {Shell Research
B.
K),
Badhuisweg 3,
1031
CMAmsterdam, The Netherlands
84, West Grove, Walton
on
Thames, Surrey KT12 5PD, UK
KoninklijkdShell-Laboratorium,
Amsterdam (Shell Research
B.
K),
Badhuisweg 3, 1031 CMAmsterdam, The Netherlands
@son
Instruments Ltd, Hatton Lyons Industrial Estate, Hatton,
Houghton-le-Spring, Tyne and Wear DH5
Om,
UK
Sievers Instruments Inc., 1930 Central Avenue, Suite
C,
Boul-
der, CO 80301, USA
Waters Chromatography Division, MiIlipore (CK) Ltd, Winster
House, Heronsway, Chester Business Park, Wrexham Road,
Chester CH4 SQR,
UK
Analytical
&
Applied Science Division, BP Research
&
Engi-
neering Centre, Sunbury-on-Thames, Middlesex,
TWI
6 7LN
UK
Siemens AG, Abt AUT 35 CHR, Postfach 21 12 62, 76187
Karlsruhe, Germany
Siemens AG, Abt AUT 35 CHR, Postfach 21
12
62, 76187
Karlsruhe, Germany
Siemens AG, Abt AUT 35 CHR, Postfach 21
12
62,
76187
Karlsruhe, Germany
Esso
Research Centre, Milton Hill, Abingdon, Oxfordshire
OX13 6AE.
UK
XVIII
1.
ROBERTS
A.T.
REVILL
S.J.
ROWLAND
A.
SIRONI
R.
TIJSSEN
G.R. VERGA
List
of
contributors
Analytical
&
Applied Science Division, BP Research
&
Engi-
neering Centre, Sunbury-on-Thames, Middlesex,
TW16
7LN,
UK
CSIRO Division
of
Oceanography, Castray Esplanade, Hobart,
Tasmania, Australia
Petroleum and Environmental Geochemistry Group, Depart-
ment
of
Environmental Sciences, Universily
of
Plymouth, Drake
Circus, Plymouth, PL4
8AA,
UK
Fisons Instruments, Strada Rivoltana,
20090
Rodano (Milan),
Italy
KoninklijkdShell-Laboratorium,
Amsterdam (Shell Research
B.
V.),
Badhuisweg
3,
I03
I
CM
Amsterdam, The Netherlands
Fisons instruments, Strada Rivoltana,
20090
Rodano (Milan),
Italy
E.R.
Adlard
(Ed.),
Chromatography
in
the Petroleum Industry
Journal
of
Chromatography
Library
Series,
Vol.
56
0
1995
Elsevier Science
B.V.
All
rights
reserved
1
CHAPTER
1
The
analysis
of
hydrocarbon
gases
C.J.
Cowper”
British Gas pfc,
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