Adlard E.R. (ed.) Chromatography in the Petroleum Industry
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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
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.
cm.
--
(Journal
of
chromatography library
;
v.
56)
p.
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.
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This book is printed
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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
5
5
8
10
10
16
16
18
19
19
21
25
25
25
26
26
27
28
29
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
52
55
55
57
57
59
60
64
65
70
75
78
81
82
84
89
90
95
95
96
96
99
100
100
102
103
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
....................................................................
127
127
128
130
131
132
133
135
137
137
138
138
139
143
143
144
146
147
147
150
151
152
152
154
155
156
157
157
159
159
160
162
164
164
164
166
167
168
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
170
171
172
172
173
173
174
174
176
177
179
180
180
181
184
184
185
187
189
190
190
191
191
192
194
195
197
197
197
197
197
200
201
201
202
203
207
209
211
213
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
.......................................................................................................
Limitations of single-column systems
.................................................
9.1.1
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
.............................................
Selectivity tuning
in
series-coupled columns
.....................................................
9.2
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
218
218
218
227
227
227
231
231
231
232
233
233
234
238
241
241
244
245
246
249
249
250
250
250
251
252
253
255
258
260
262
263
263
266
266
269
269
271