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 Fabrice BERTONCINI
IFP Energies nouvelles

Marion COURTIADE-THOLANCE
IFP Energies nouvelles

Didier THIÉBAUT
CNRS – ESPCI ParisTech

GAS CHROMATOGRAPHY
AND 2D-GAS CHROMA
FOR PETROLEUM INDUSTRY
THE RACE FOR SELECTIVITY

Translated from the French

by Trevor Jones (Lionbridge)

2013

Editions TECHNIP 25 rue Ginoux, 75015 PARIS, FRANCE

FROM THE SAME PUBLISHER

Biofuels
Meeting the Energy and Environmental Challenges of the Transportation Sector
D. BALLERINI

Hydrogen, the Post-Oil Fuel?

E. FREUND, P. LUCCHESE

Select Thermodynamic Models for Process Simulation

A Pratical Guide using a Three Steps Methodology
J.C. DE HEMPTINNE, J.M. LEDANOIS, P. MOUGIN, A. BARREAU

Heavy Crude Oils

From Geology to Upgrading. An Overview
A.Y. HUC

CO, Capture
Technologies to Reduce Greenhouse Gas Emissions
J. LECOMTE, P. BROUTIN, E. LEBAS

Multiphase Production
Pipeline Transport, Pumping and Metering
J. FALCIMAIGNE, S. DECARRE

Corrosion and Degradation of Metallic Materials

Understanding of the Phenomena and Applications in Petroleum and Process
Industries
F. ROPITAL

A Geoscientist’s Guide to Petrophysics

B. ZINSZNER, EM. PERRIN

Acido-Basic Catalysis (2 vols.)

Application to Refining and Petrochemistry
C. MARCILLY

Petroleum Microbiology (2 vols.)

J.P. VANDECASTEELE

Physico-Chemical Analysis of Industrial Catalysts

A Practical Guide to Characterisation
J. LYNCH

Chemical Reactors
From Design to Operation
P. TRAMBOUZE, J.P. EUZEN

Petrochemical Processes (2 vols.)

Technical and Economic Characteristics
A. CHAUVEL, G. LEFEBVRE

All rights reserved.

No part of this publication may be reproduced or transmitted in any form or by any means, electronic or
mechanical, including photocopy, recording, or any information storage and retrieval system, without the
prior written permission of the publisher.

0 Editions Technip, Paris, 20 13.

Printed in Frunce
ISBN 978-2-7108-0992-0
 Preface

The field of comprehensive two-dimensional gas chromatography (GC×GC) has undergone

a significant evolution since its inception. The first decade of development focused prima-
rily on improvements in the instrumentation, as the technology moved from proof-of-con-
cept prototypes in the laboratory to commercial instruments. The past decade has shifted
towards improvements in the scope of the technique, and has seen a growth in the number of
different application areas (petroleum, bioanalytical, environmental, etc.). The goal of
GC×GC applications is a substantial improvement in the elucidation of a variety of complex
samples beyond the analyses that are currently achievable using conventional gas chroma-
tography (GC). A strong debate still abounds as to the figures of merit of the current GCxGC
state-of-the-art on the market, particularly since there are still relatively significant develop-
ments to be achieved in terms of instrumentation efficiency and particularly advanced soft-
ware features. However, the growing number of GC×GC applications are revealing that the
scope of this technology is well worth the continued investment.
The petroleum industry is a very important application area for GC×GC, as demonstrated
by the percentage of peer-reviewed papers that have been published in the past 20 years. The
selectivity capabilities of GC×GC that allow for the ordered dissemination of molecular
structure gradients along the two-dimensional separation space are particularly effective in
enhancing the qualitative and quantitative resolution of samples in a manner not possible
with current high-resolution GC technology. As the industry moves towards the new chal-
lenges that surround the need to develop alternative production routes for fuel or petroleum
derivatives (biomass conversion, etc.), the fractions to be analyzed are increasing in their
complexity and are stretching the capabilities of GC×GC even when combined with mass
spectrometry. This situation has thus ushered the need to explore couplings of the core tech-
nology with other modules to further improve the dimensionality of the analyzer. I firmly
believe that the next decade will see the establishment of GC×GC as a premier separation
science technology, and that petroleum industry applications will play a critical role in the
expansion of multidimensional chromatographic strategies.
I have had the distinct privilege to be associated with GC×GC since its inception in the
Phillips laboratory in 1989, and have enjoyed witnessing and working on a number of excit-
ing developments in the technique. The group of authors from IFP Energies Nouvelles
(IFPEN) and the École Supérieure de Physique et de Chimie Industrielles de la Ville de
Paris (ESPCI ParisTech) laboratories that have teamed up in this effort have, over the past
decade, steadily worked on improving the capabilities of GC×GC to solve practical prob-
lems in the petroleum industry, and it has been very gratifying to interact with them over the
years, primarily as a reviewer of projects that have been written up into five PhD disserta-
tions and over thirty peer-reviewed manuscripts to date.
VI Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

Under the direction and supervision of Fabrice Bertoncini, Marion Courtiade and their
colleagues (at IFPEN) and Marie-Claire Hennion and Didier Thiébaut (at ESPCI ParisTech
and the Centre National de la Recherche Scientifique -CNRS) the work of their PhD and
post-doctoral researchers has dealt with a variety of important fundamental concepts (cen-
tered around GC×GC modulation and orthogonality) as well as the innovative inclusion of
techniques aimed at increasing the dimensionality of the GC×GC instrument pre- and post-
analysis (i.e. supercritical fluid chromatography, and data processing software).
This book represents a collective review to these individual projects combined with an
overview of recent advances in GC and related techniques to cope with more complex media
to be separated. The common goal of these investigations is quite simply the improvement
of molecular information via the increase of separation power. The first few chapters are
very didactic in nature and are intended to be used as a general introduction to GC×GC the-
ory, instrumentation, and data processing. The latter book chapters then focus more specifi-
cally on applications of GC and GC×GC in the petroleum industry, from detailed hydrocar-
bon analysis to global properties calculations.
Other books on GC×GC have appeared in the past few years, but the strength of this
body of work resides in the combined development of technology and application strategies
by a cohesive group of scientists, as opposed to a compendium of individual researchers
contributing single chapters. This approach will be very welcome in a field that is still grow-
ing but in need of monographs that help the expanding number of new users while satisfying
the existing experts to push the boundaries of their current conceptual understanding of the
technique so that it can help them develop the next generation of instruments and methods.
The field of multidimensional separation science is an exciting field that is still in develop-
ment, and I truly believe that this contribution will be a worthy reference in everyone’s
library.
Jean-Marie D. Dimandja
Department of Chemistry and Biochemistry
Spelman College
Atlanta, USA
December 2012
 Table of Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII

List of authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IX

List of abbreviations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XV

Chapter 1
Molecular Analysis for Petroleum Products: Challenges and Future Needs
Fabrice Bertoncini (IFP Energies nouvelles)
1.1 Overview on the Nature of Petroleum Oil and its Components. . . . . . . . . . . 1
1.1.1 Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 Heteroatom Containing Family . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2.1 Sulphur Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1.2.2 Nitrogen Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.2.3 Oxygenated Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.3 Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.4 Resins/Asphaltenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.1.5 Biomarkers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2 Crude Oil Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.2.1 Basic Refining Treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.1.1 Gasoline Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.2.1.2 Distillate Hydrotreating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2.1.3 Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2.2 Conversion of Heavy Ends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.2.3 Visbreaking and Thermal Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.4 Coking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.5 Fluid Catalytic Cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.6 Hydrocracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.2.7 From Future Trends for Refining to New Challenges in Molecular Analysis . . . . 13
1.2.7.1 Trends for Refining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.2.7.2 Challenges in Molecular Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.3 Molecular Analysis at Different Scales. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
1.3.1 From Global Analysis to Detailed Analysis of Petroleum Products . . . . . . . . . . . 17
1.3.2 Global Characterisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.3.3 Elemental and Structural Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
XVIII Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

1.3.4 Hydrocarbon Family Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

1.3.4.1 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.3.4.2 Liquid Phase Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.3.4.3 Supercritical Fluid Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.3.5 Molecular Analysis by Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.5.1 Brief History of Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
1.3.5.2 Simulated Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.3.5.3 Detailed Analysis of Gaseous Hydrocarbons . . . . . . . . . . . . . . . . . . . . . 24
1.3.5.4 Detailed Analysis of Liquid Hydrocarbon . . . . . . . . . . . . . . . . . . . . . . . 24
1.3.5.5 Heteroelements Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3.5.6 Mass Detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.3.6 Improving the Separation Capacity: Multidimensional Gas Chromatography . . . . . 29
1.3.6.1 Valveless Based System (Deans’ Type Device) . . . . . . . . . . . . . . . . . . . 31
1.3.6.2 Interest of MDGC for Molecular Analysis . . . . . . . . . . . . . . . . . . . . . . . 32
1.3.6.3 Applications of MDGC for Molecular Analysis of Petroleum Derivatives . 33
1.3.7 State of Art of Conventional Molecular Analysis vs Analytical Challenges . . . . . . 36
1.3.8 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38

Chapter 2
×GC: a Disruptive Technique
GC×
Thomas Dutriez (DSM Resolve)
2.1 Multidimensional Chromatographic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.1.1 Complex Mixtures: Limitation of 1D Chromatography . . . . . . . . . . . . . . . . . . . . 43
2.1.2 Basic Principles of Multidimensional Systems . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.1.2.1 Orthogonality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.1.2.2 Sample and System Dimensions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.1.3 Difference between Heart-cutting and Comprehensive Coupling . . . . . . . . . . . . . 46
2.1.3.1 Heart-cutting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.1.3.2 Comprehensive Coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.2 Theoretical Aspects Related to GC× ×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2.1 Operating Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
2.2.2 Modulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.2.1 Modulation Phenomenon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2.2.2.2 Sampling Frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
2.2.2.3 Influence on Separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
2.2.3 Chromatographic Aspects Related to GC×GC. . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.2.3.1 Column Combination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.2.3.2 Determination of Retention Indices . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.2.4 Two-dimensional Separation Evaluation Criteria . . . . . . . . . . . . . . . . . . . . . . . . 61
2.2.4.1 2D Resolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.2.4.2 Orthogonality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.2.4.3 Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2.2.4.4 2D Asymmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.3 GC× ×GC Specific Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3.1 Modulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3.1.1 Thermal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
2.3.1.2 Cryogenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
 Table of Contents XIX

2.3.1.3 Valve-type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.3.1.4 Comparison of Modulators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3.2 Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3.2.1 Universal and Selective Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
2.3.2.2 Detection by Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
2.4 Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.5 Choice of Separation Conditions in GC× ×GC . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.5.1 Selection of Stationary Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.5.2 Column Dimensions vs Modulation Period . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.5.3 Kinetic Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
2.5.4 Temperature Regime. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.5.5 Influence of Operating Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.5.6 Predictive Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2.6 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86

Chapter 3
×GC. Applications to the Petroleum Industry
Data Processing Applied to GC×
Benoît Celse, Maxime Moreaud, Laurent Duval (IFP Energies nouvelles),
Daniela Cavagnino (Dani Instrument Spa)
3.1 Basis of Signal Processing in Chromatography . . . . . . . . . . . . . . . . . . . . . . . . 99
3.1.1 Baseline Suppression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.1.1.1 General Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.1.1.2 Recommended Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.1.2 Detection of Chromatogram Elution Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.1.2.1 Calculating Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
3.1.2.2 Deconvolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.1.2.3 Morphological Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
3.1.2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3.1.3 Identification of Chromatogram Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
3.1.4 Global Comparison of Chromatograms (Fingerprint Type Analysis) . . . . . . . . . . 108
3.1.4.1 Signal Synchronisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.1.4.2 Comparison of Chromatograms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
3.2 General Presentation of Signal Processing Techniques Applied to GC× ×GC 114
3.2.1 Description of the Chromatograms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
3.2.2 Specificities of 2D Chromatograms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
3.2.3 Description of the Various GC×GC Utilisation Methods . . . . . . . . . . . . . . . . . . 118
3.3 Determination of the Concentration of Compounds
or Pseudo-compounds in GC× ×GC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3.3.1 General Description of the Quantitative Analysis Numerical Methods . . . . . . . . . 119
3.3.1.1 Manual Determination of Blobs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
3.3.1.2 Automatic Determination of Blobs by Application of Rules . . . . . . . . . . 120
3.3.1.3 Automatic Determination of Blobs by Image Processing . . . . . . . . . . . . 120
3.3.1.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
3.3.2 Baseline Suppression . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
3.3.3 Determination of “raw” Elution Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
XX Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

3.3.4 Identification of Blobs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122

3.3.4.1 Definition of a Reference Template . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
3.3.4.2 Adaptation of the Template to a New 2D Chromatogram. . . . . . . . . . . . . 124
3.3.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
3.4 Illustrations of Quantitative Analysis of Data Obtained by GC× ×GC . . . . . . . 127
3.4.1 Quantification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.4.1.1 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.4.1.2 Analytical System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.4.1.3 Template Construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3.4.1.4 Comparison between Automatic and Manual Recalibration . . . . . . . . . . . 132
3.4.2 Mixtures Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3.4.2.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
3.4.2.2 Illustration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
3.4.3 Simulated Distillation Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
3.4.4 Simulation of Physical Cuts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
3.4.5 Calculations of Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.4.5.1 Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.4.5.2 Principle of Property Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.4.5.3 Application Example . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
3.5 Comparison of GC× ×GC Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.5.1 Interest of Fingerprint Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.5.2 Types of Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
3.5.3 Pre-processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.5.4 Comparison by Studying 3D Peaks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.5.4.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.5.4.2 Application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
3.5.5 Comparison by Application of a Template . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.5.6 Multi-sample Comparison . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
3.6 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

Chapter 4
×GC Dimension
Coupled Systems with a GC or GC×
Thomas Dutriez (DSM Resolve)
4.1 Overview of Requirements and Coupling Possibilities. . . . . . . . . . . . . . . . . . . 159
4.1.1 Chromatographic Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
4.1.2 Coupling Possibilities with GC or GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.1.3 Practical Implementation of Highly Hyphenated System . . . . . . . . . . . . . . . . . . . 161
4.1.3.1 Interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
4.1.3.2 Specificity of Comprehensive Coupling Systems . . . . . . . . . . . . . . . . . . 162
4.2 Systems with a GC Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.2.1 Coupling between an LC Dimension and GC . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.2.1.1 LC-GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
4.2.1.2 LC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
4.2.2 Coupling between an SFC Dimension and GC . . . . . . . . . . . . . . . . . . . . . . . . . . 170
4.2.2.1 SFC-GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
4.2.2.2 SFC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
4.2.3 Summary Table of Relevant Petroleum Applications . . . . . . . . . . . . . . . . . . . . . . 173
 Table of Contents XXI

4.3 Systems with a GC× ×GC Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175

4.3.1 Coupling between a GC Dimension and GC×GC . . . . . . . . . . . . . . . . . . . . . . . . 175
4.3.1.1 GC-GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
4.3.1.2 GC×GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
4.3.2 Coupling between an LC Dimension and GC×GC . . . . . . . . . . . . . . . . . . . . . . . 177
4.3.2.1 LC-GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
4.3.2.2 LC×GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
4.3.3 Coupling between an SFC Dimension and GC×GC . . . . . . . . . . . . . . . . . . . . . . 180
4.3.4 Summary Table of Relevant Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
4.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

Chapter 5
Detailed Analysis of Hydrocarbons
Frederick Adam (Saudi Aramco) and Thomas Dutriez (DSM Resolve)
5.1 Analysis of Diesel Cuts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.1.1 Conventional Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.1.2 Target Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
5.1.2.1 Analysis of Biodiesel and Diesel Blends. . . . . . . . . . . . . . . . . . . . . . . . 191
5.1.3 Extended PIONA Analysis of Middle Distillates by GC×GC . . . . . . . . . . . . . . . 193
5.1.3.1 Orthogonal Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
5.1.3.2 Non-orthogonal Approach. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
5.1.3.3 Quantitative Comparison with the Reference Methods . . . . . . . . . . . . . . 196
5.1.4 Towards a Third Separation Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
5.1.4.1 Third Separation Dimension by Detection . . . . . . . . . . . . . . . . . . . . . . 198
5.1.4.2 Adding a Separation Dimension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
5.1.5 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
5.2 Analysis of Heavy Petroleum Fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
5.2.1 Global Group Type Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
5.2.2 Group Type Analysis for Heteroelement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
5.2.2.1 Sulphur Speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
5.2.2.2 Nitrogen Speciation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
5.2.3 Target Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
5.2.4 Summary Table of Applications to Petroleum Products . . . . . . . . . . . . . . . . . . . 216
5.3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216

Chapter 6
Calculating Properties from Chromatographic Data
Cyril Dartiguelongue, Vincent Souchon and Benoît Celse (IFP Energies nouvelles)
6.1 Property Prediction Based on One-dimensional GC – RON and MON
Octane Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
6.1.1 The Octane Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
6.1.2 Determination of Octane Number from Chromatographic Data . . . . . . . . . . . . . . 227
6.1.2.1 Linear Octane Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
6.1.2.2 Non-linear Octane Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
6.1.2.3 Octane Profiles and Cumulated RON . . . . . . . . . . . . . . . . . . . . . . . . . . 233
XXII Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

6.2 Predicting Properties Using Two-dimensional Data – Example of the

Cetane Number . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
6.2.1 Cetane Number: Definition, Measurement and Prediction . . . . . . . . . . . . . . . . . . 235
6.2.2 Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
6.2.2.1 Description of Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
6.2.2.2 GC×GC Analysis/Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
6.2.2.3 Strategy for Cetane Model Development . . . . . . . . . . . . . . . . . . . . . . . . 242
6.2.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
6.2.3.1 Comparison of GC×GC Results with Conventional Techniques . . . . . . . . 243
6.2.3.2 Cetane Model from GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
6.2.3.3 Application to Virtual Samples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
6.2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
6.3 Other Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
6.3.1 Property Models Based on GC Analysis of Gasolines . . . . . . . . . . . . . . . . . . . . . 253
6.3.1.1 Examples of Linear Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
6.3.1.2 Examples of Non-linear Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
6.3.2 Properties Modelling from GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
6.3.2.1 Molecular Weight Calculation from GC×GC/FID . . . . . . . . . . . . . . . . . . 255
6.3.2.2 Viscosity Prediction of Fuels Using a Molecular-based Approach . . . . . . 256
6.4 Conclusion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257

Chapter 7
Speciation of Heteroelements
7.1 Speciation of Sulphur. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
Laure Boursier (IFP Energies nouvelles)
7.1.1 Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
7.1.1.1 Specific Sulphur Detectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
7.1.1.2 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
7.1.2 GC×GC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
7.1.2.1 Pre-separation between Sulphur Compounds and Hydrocarbon Matrix . . . 269
7.1.2.2 Specific Sulphur Detectors Adaptable to GC×GC . . . . . . . . . . . . . . . . . . 270
7.1.2.3 Application to Petroleum Matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
7.2 Speciation of Nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
Marion Courtiade-Tholance (IFP Energies nouvelles)
7.2.1 Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
7.2.1.1 Hall Electrolytic Conductivity Detector . . . . . . . . . . . . . . . . . . . . . . . . . 275
7.2.1.2 Thermionic Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
7.2.1.3 Atomic Emission Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
7.2.1.4 NCD Detector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 277
7.2.2 GC×GC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
7.3 Speciation of Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
Badaoui Omais (IFP Energies nouvelles)
7.3.1 Speciation of Oxygen in Coal-derived Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.3.1.1 Properties of Coal-derived Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
7.3.1.2 1D Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
7.3.1.3 GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
 Table of Contents XXIII

7.3.2 Speciation of Oxygenates in Fischer-Tropsch Products . . . . . . . . . . . . . . . . . . . 296

7.3.2.1 Gas Chromatography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 297
7.3.2.2 GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 299
7.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 300

Chapter 8
Simulated Distillation
Didier Thiébaut (ESPCI)
8.1 Physical Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311
8.2 Gas Chromatography Simulated Distillation (Simdis) . . . . . . . . . . . . . . . . . . 312
8.2.1 Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.2.1.1 Calibration Step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.2.1.2 Injection Step. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312
8.2.1.3 Reprocessing Step . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
8.2.2 Implementation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
8.2.2.1 Type of Chromatographic Column . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
8.2.2.2 Type of Stationary Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
8.2.2.3 Routine Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.2.3 Applications of Simdis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
8.2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.3 Simulated Distillation by GC× ×GC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.3.1 Simulated Distillation of Gas Oils by GC×GC . . . . . . . . . . . . . . . . . . . . . . . . . . 318
8.3.1.1 Simulated Distillation by Hydrocarbon Family . . . . . . . . . . . . . . . . . . . 319
8.3.1.2 Application to Monitoring of Conversion Processes . . . . . . . . . . . . . . . 322
8.4 Simulated Distillation by LC-GC× ×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 323
8.5 Simulated Distillation by SFC-GC× ×GC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
8.6 Simulated Distillation by Supercritical Fluid Chromatography (SFC) . . . . 326
8.6.1 Experimental Part – Caution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
8.6.2 Packed Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
8.6.3 Open Tubular Capillary SFC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337
1 Molecular Analysis for Petroleum
Products: Challenges and
Future Needs
Fabrice Bertoncini (IFP Energies nouvelles)

1.1 OVERVIEW ON THE NATURE OF PETROLEUM OIL

AND ITS COMPONENTS

Petroleum Oil is a complex mixture consisting of a very large number of various hydrocarbon
molecules including or not heteroatom such as sulphur, nitrogen or oxygen, but also metals.
Main elements remain carbon (≈ 80% w/w) and hydrogen (≈ 10-15% w/w). The proportion of
heteroatom frequently depends on the geological origin of oil, e.g. degree of maturity, in par-
ticular for the sulphur and nitrogen contents (Table 1.1). These differences in composition
induce variable physico-chemical properties (e.g. density) and imply conditions of production
and transformation which are dependent on the molecular nature of crude oils. Therefore, the
need for reaching their composition the most accurately possible is a critical challenge.
Table 1.1. Average elemental composition of crude oils according to the geographic origin [Wauquier JP, 1994].

O N S Ni V
Origin
(kg/kg) (kg/kg) (kg/kg) (mg/kg) (mg/kg)
Batiraman (Turkey) 0.5 0.5 7.0 99 153
Boscan (Venezuela) 0.8 0.7 5.5 125 1,220
Chauvin Source (Canada) 0.5 0.7 2.8 35 67
Anguille (Democratic Republic of Congo) 1.1 0.7 0.6 64 9

1.1.1 Hydrocarbons

The hydrocarbons, molecules only made up of carbon and hydrogen, are the majority com-
ponents of petroleum oil. The proportions of the different molecules vary widely from one
crude to another, as do the levels of impurities. The hydrocarbon molecules that can be
found range from methane (C1) to the heaviest molecules (with a hundred carbon atoms, or
even more). A distinction by chemical families may be carried out according to the presence
of unsaturated bonds (Table 1.2). Thus, the saturated alkanes or aliphatic hydrocarbons can
be distinguished in normal paraffin (linear) and iso-paraffin (ramified). Also present, the
2 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

saturated cyclic-alkanes or naphthenes can contain several cycles and/or alkyl chains.
Lastly, the aromatic hydrocarbons, mono or polycyclic structures, can be or not alkylated
and/or contain a condensed cyclic naphthene. Not present in crude oils or cuts of direct dis-
tillation, the unsaturated hydrocarbons or olefins can come from conversion processes.

Table 1.2. Structures of hydrocarbon compounds in the petroleum oil.

Hydrocarbon family Formula Example of developed structure

n-paraffin CnH2n+2

Iso-paraffin CnH2n+2

Olefin CnH2n

Naphthene CnH2n

Aromatics CnH2n-6k ou CnH2n-8k

n: carbon atom number.

k: aromatic cycle number.

Unlike lighter fractions, in which the hydrocarbon structures are mainly aliphatic (paraf-
fins with some mono and di-naphtenes) or monoaromatics, heavy fractions rather include
naphtenic and aromatic structures with more than six alkylated cycles. The aromatic content
increases with the boiling point, as well as the number of aromatic cycles in the structures.
The aromatic distribution of Vacuum Gas Oil (VGO, 350-550°C) fractions is mostly centred
on structures including from 1 to 3 polyaromatic cycles, whereas structures of residues
(550°C+) mainly contain polyaromatics of 5-6 cycles. The higher the boiling point is, the
more enriched in heteropolyaromatic structures the fractions are [Merdrignac I and
Espinat D, 2007].

1.1.2 Heteroatom Containing Family

1.1.2.1 Sulphur Compounds

The most widespread heteroatom in crude oils is sulphur, whose content is strongly corre-
lated with the density of the oil cuts. Thus, the major part of the sulphur compounds is
present in the heavy cuts. The sulphur compounds generate many problems because they are
at the origin of atmospheric pollutions (SO2 and SO3) and are proven to be poison for cata-
lysts containing noble metals (refining processes or automotive’s pollution). The sulphur
content in the on-road fuels is therefore unceasingly decreasing, to the minimum of
10 mg/kg in 2010 for on road Diesel fuel and gasoline (EN228 and EN590 European speci-
fications, respectively). The sulphur compounds (Table 1.3) contained in the petroleum oil
matrices can be differentiated as various chemical families: sulphides or disulphides (R-S-R
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 3

or R-S-S-R), thiols or mercaptans (R-SH) – acid and corrosive compounds, especially

present in the lightest fractions- and thiophenic derivatives.
Thiophenes are condensed polyaromatic structures with benzo-, dibenzo-, naphtobenzo-
and other derived structures.
Sulphur compounds contained in residues are similar to sulphur species in lighter frac-
tions, but in different proportions. In heavy fractions, major sulphur species are the
thiophenics, followed by sulphide derivatives (cyclic and acyclic). Only small amounts of
sulfoxide types are detected.

Table 1.3. Structures of sulphur compounds in the petroleum oil.

Family Example Family Example

Mercaptan or thiol SH Benzothiophen

S

Sulphide S Dibenzothiophen
S
Disulphide S
S
Naphtodibenzothiophen
Thiophen
S
S

1.1.2.2 Nitrogen Compounds

Although nitrogen content in heavy crudes appears to be much lower than other heteroele-
ments, it has a large influence in hydrotreatment processes as it induces catalyst poisoning.
Two classes of nitrogen compounds are distinguished (Table 1.4):
– compounds presenting a neutral character and including a pyrrolic-based structure
(5 atoms) or a amide function,
– basic compounds presenting a pyridinic cycle (6 atoms) or a NH2 function (amines or
aniline).
This distinction is of major importance because the basic nitrogen derivatives are known
to poison acid catalysts. The neutral derivatives are also alleged to be poisons for acid cata-
lysts, but also refractory towards hydrotreating. They can also be at the origin of the gum
formation at the time during operations of refining.
The major basic nitrogen families characterised in 350°C+ fractions are quinolines struc-
tures containing from 2 to 4 aromatic cycles with different configurations (peri- or catacon-
densed with various alkylation degrees). Among them, the presence of benzo-, dibenzo-,
tetrahydro-quinoleines and azapyrenes have been identified [Igniatiadis et al., 1985].
Concerning the neutral structures, a majority of carbazoles, benzo- and dibenzo-carbazoles
families with different alkylation degrees were detected [Dorbon et al., 1982].
4 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

Table 1.4. Structures of basic and neutral nitrogen compounds present in the petroleum oil products.

Neutral N-compound Basic N-compound

Family Example Family Example
NH2
Pyrrole Aniline
N

H N
Indole N Pyridine

H
N N
Carbazole Quinoleine

NH N
Amide O Acridine

1.1.2.3 Oxygenated Compounds

Among the oxygenated compounds present in the oil products, it can be distinguished
the carboxylic naphtenic acids, often present in the middle distillates cuts, and esters, phe-
nols, furans and benzofurans which are rather present in the Vacuum Gas Oil (VGO) or
heavier cuts [Moschopedis and Speight, 1976]. Although not very present, the oxygenated
compounds having an acid character can generate problems of corrosion and are responsible
for the total acidity of crude oils. In addition, the oxygenated compounds are present in
greater quantity in the cuts resulting from the biomass and coal (see Section 7.3).

1.1.3 Metals
Metals like vanadium or nickel are mainly present in the heaviest fractions in the form of
complexes with porphyrin molecules type [Wauquier JP, 1994]. They can be at the origin of
the poisoning of catalysts used for the conversion of the residues.
Al, Si, Mo, Sn, Ni, Co could be released by catalysts, and Al, Mn, Cu, Cr, Fe, Ni, Zn
could be released by tubings and the different metallic parts that could corrode and be
degraded during operation. Their presence could reveal operation problems that need repair-
ing as soon as their detection has been shown. Cu, Cd, Si, As and Pb are elements affecting
catalyst’s efficiency coming from different origins. They could be native in the petroleum
crude or added in the refinery scheme by pollution or for a precise purpose. Their presence
and identification in feeds are highly needed in order to avoid further poisoning of the differ-
ent catalysts present in a refinery.
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 5

1.1.4 Resins/Asphaltenes
The heaviest oil cuts comprise polar non-volatile components: resins and asphaltenes. Not
being able to determine their structural or chemical characteristics strictly, they are fre-
quently defined by purely operational conditions or physic measurement. The general defi-
nition presents asphaltenes like the insoluble fraction of an oil matrix in a paraffinic solvent
(n-heptane or n-pentane). The resins are the most polar compounds of their soluble fraction
in same solvent. The structural composition of these very polar fractions, which can repre-
sent between 20 and 40% w/w of a crude oil (Figure 1.1), is still badly known. It is accepted
that they are mainly composed of condensed polyaromatic hydrocarbons of molecular mass
500-1,000 for resins and 1,000-100,000 for asphaltenes.

100

90
Saturates
Volatile
80 saturate/
Aromatics
70

60 Aromatics
Feedstock (%)

50
Nonvolatile
saturate/
40 Aromatics

30
Polar-
Resins aromatics
20

10
Asphaltenes
0
0 20 40 60 80 100
(wt %)

Figure 1.1
Mass distribution of a crude oil according to the chemical structures saturated,
aromatic, resins and asphaltenes [adapted from Speight JG, 2004].

Asphaltenes are thus regarded as the components of the crude oil of higher molecular mass
and of the highest polarity. They can be defined like molecules with various degrees of con-
densations (their aromatic fraction represents approximately 50% of the carbon total amount)
having properties of self-association and aggregation. Because of their very great hetero-
geneity, there does not exist a single structural pattern and various models were advanced to
describe these structures, such as continental or archipelago type [Merdrignac I and Espinat D,
2007]. Taking into account this complexity, the characterisation of asphaltenes remains a real
6 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

analytical challenge [Merdrignac I and Espinat D, 2007]. Moreover, the yields of the separa-
tion are very dependent on the experimental conditions (influence of the state of aggregation).
The analytical techniques used for asphaltenes are under the scope of this chapter; nevertheless
it can be outlined that several techniques of colloidal characterisation can be employed such as
techniques of diffusion, Nuclear Magnetic Resonance (NMR) or Steric Exclusion Chromatog-
raphy (SEC).
The resin fractions play a crucial role in the stability of oil cuts by preventing the decom-
position of asphaltenes. They are separated from the maltene fraction (resins + oil) after
deasphalting. The compounds present in the resin fraction are regarded as aromatic, whereas
their total polarity is only a little weaker [Speight JG, 2004]. A variety of hydrocarbon struc-
tures is present there including nitrogen, sulphur and a big amount of oxygen (esters, acids
and carbonyls).

1.1.5 Biomarkers
Often present in small quantity, the biomarkers represent the degree of maturity of a crude
oil. Their nature and proportion will be dependent on its geographic origin. Those are
largely used for geological investigations but also to identify the origins of a pollution.
Peters et al. [Peters KE et al., 2005] thus define the various structures of the biomarkers
most usually found in crude oils, like aromatic compounds such as chrysenes, alkyl-naph-
thalen, phenanthren, and sulphur compounds such as dibenzothiophens and benzonaph-
tothiophens. It can also be noticed that some saturated structures like the isoprenoïdes,
cyclic or acyclic paraffinic structures are highly ramified. Among the acyclic saturated
biomarkers usually met in the average distillates, the prystane (C19 carbon atoms) or the
phytane (C20) can be distinguished. For the heavier cuts, it can be met the squalanes (C30),
the biphytanes (C40), the licopane (C40). For the polynaphtenic structures from the heavy
cuts, the three great types are the steranes (derivatives of sterol, tetracyclic forms), triter-
panes (derivatives of terpenoïdes being able to be tri-structures, tetra or pentacyclic) and
finally hopanes (pentacyclic structures).

1.2 CRUDE OIL REFINING

Crude oil refining consists in separating and transforming the crude oils extracted from
various origins into valuable products such as on road fuel transportation (gasoline, Diesel
fuel, kerosenes or marine fuels), intermediaries for the petrochemicals or others (oils, bitu-
mens…). The various operations will make it possible to obtain products answering the
specifications in term of environmental aspect (e.g. content of sulphur or aromatic com-
pounds), of performance aspect and in term (octane number, cetane number) whatever their
origin that can be grouped as follows:
– separation of crude oil into different fractions by separation operations, including
atmospheric, vacuum distillation and, in some cases, such as for lube manufacturing,
solvent extraction;
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 7

– chemical conversion of fractions resulting from separation, to produce base products

for the end-use products such as fuels, heating oils, and specialty products;
– improvement of the quality of most of the fractions to meet current and future regula-
tions on end-use products, for example regulations on sulphur content;
– conversion of heavy fractions, which cannot be utilised directly, into light fractions,
again for use as base products for end-use products; as a general rule, these light frac-
tions resulting from conversion must also undergo post-treatment of greater or lesser
severity to improve their quality and make them compatible with current and future
regulations;
– final preparation of end-use products by blending, plus, if required, enhancement of
some properties with additives, i.e.; cold flow properties, cetane improvers, anti-static
additives, lubricity improvers, viscosity index improvers, stabilisers, etc.
An effort is particularly carried out for an optimisation of the production in order to
answer at the request of the market towards the light products. Taking into account the
increasingly part of heavy crude oil, unit operations of conversion of the heavy cuts are
gradually installed in refinery.
Preceded by a desalting step to remove minerals, the crude distillation unit constitutes
the first and the principal stage of the refining.
The principle of distillation is that the boiling point of a molecule increases with the size,
and therefore with the number of carbon atoms. An atmospheric distillation column can thus
separate light fractions up to gasoline. These light fractions are then separated, in smaller
capacity columns, into fuel gas (methane, ethane), propane, butane, light gasoline (also
called light naphtha) and heavy gasoline (also called heavy naphtha):
– a kerosene fraction, used for producing aviation fuel, solvents and light heating oils;
– an Atmospheric Gas Oil (AGO) fraction used for producing Diesel fuel for vehicles or
domestic heating oil, or off-road motor fuel for certain applications, including agricul-
tural and civil engineering machinery, trains and boats;
– an Atmospheric Residue (AR) which generally requires a large amount of processing
to convert it into base products for end-use products;
– a vacuum distillation (in order to avoid the cracking of C-C bound beyond 400°C) of
the residues is then carried out to tap a cut of valuable product: the Vacuum Gas Oil
(Figure 1.2). The Vacuum Residues (VR) are composed of the majority of the impuri-
ties of the crude, in particular the totality of asphaltenes, and are used for the manu-
facturing of the bitumens or heavy fuels or they can also be converted into lighter
products by conversion processes.
The total properties of each cut are presented in Table 1.5. Each cut corresponds to a
range of boiling point corresponding to a range of an equivalent carbon atoms of paraffin.
Their proportion is dependent on the geographical origin of crude oil and the considered
cuts. It is noticed that the evolution of the density, of the proportion of sulphur and nitrogen
is related to the interval of distillation of the cuts.
8 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

Atmospheric
Distillation

Gas
C1-C4(35°C-)
Crude
oil Gasoline
C5-C10 (35-175°C)
Vacuum
distillation
Kerosene
C10-C13 (175-235°C)

Middle distillate
C13-C25 (235-400°C)

Atmospheric Residue Vacuum gas oil

C20+(350+) C20-C60
(350-600°C)

Vacuum residue
C50+ (550+)

Figure 1.2
Atmospheric and vacuum distillations of a crude oil.

Table 1.5. General characteristics of main cuts from crude oil distillation (Arabian light) [Wauquier JP, 1994].

Gasoline
Oil cuts Gas or Kerosene Diesel VGO VR
naphtha
Boiling point (°C) <0 0-180 180-230 230-375 375-600 600+
Average carbon
C1-C4 C4-C10 C10-C14 C14-C25 C25-C55 > C55
atom number
Yield (kg/kg) 1.37 17.72 6.74 24.37 23.50 26.30

Density ( d415 ) 0.654 0.742 0.793 0.851 0.935 1.037

Sulphur (kg/kg) 0.003 0.035 0.150 1.4 2.8 5

Nitrogen (mg/kg) – – – – ≈ 1,000 ≈ 3,500
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 9

The oil cuts, thus separated, are modified or converted to obtain the most important part of
valuable fuel (Figure 1.3). A crude oil is thus all the more interesting as it would be rich in
light cuts (e.g. those coming from the North Sea), because requiring less stages of conversion.

LPG
Naphtha

Light naphtha
Isomerisation iC4
Atmospheric distillation

Crude oil Heavy naphtha

Reformer Gasoline

C4=
H2 Alkylation
Sweetening
Jet fuel
or HDS

Atmospheric gas oil

HDS Diesel

Vacuum distillate
FCC LCO H2

Atmospheric Heavy
Vacuum HCO fuel oil
residue
distillation

Visbreaker
Vacuum residue

Figure 1.3
Oil refining simplified diagram – conversion processes for gasoline oriented
refinery.

1.2.1 Basic Refining Treatments

1.2.1.1 Gasoline Treatment

The heavy gasoline produced by distillation has a very low octane number (40 to 50, as
against a specification, i.e. a required quality, of 92 to 95). This gasoline is therefore treated
in a catalytic reforming facility, where the saturated, paraffin and naphthenic molecules are
cyclised and dehydrogenated (“reformed”) into aromatics in order to increase their octane
rating. Light gasoline can be treated by another catalytic process, isomerisation, to increase
its octane number. For these two processes, the specifications for the nitrogen and sulphur
content of the feedstock are very strict (< 0.5 or 1 mg/kg), and pre-treatment is therefore
required by catalytic hydrotreating on a metal sulphide catalyst on an alumina support.
Because of the reactivity of the feedstock, the operating conditions (temperature, residence
time and hydrogen pressure) are smooth.
10 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

1.2.1.2 Distillate Hydrotreating

The sulphur contained in nearly all refinery products must also be removed. The specifications
for maximum sulphur content are now so strict that, with the exception of certain products such
as base oils, bitumens and some heavy fuels and bunker oils (to be changed in the near future for
that products), all fractions must be hydrodesulphurised, in other words treated with hydrogen
which combines with sulphur to give H2S. Here again, catalytic hydrotreating (HDT) processes,
using metal sulphide catalysts on alumina, are essential. The operating conditions become more
severe for higher molecular weights of the fraction to be treated; in other words, for fractions
which are heavier in terms of the distillation range and have a higher aromaticity.

1.2.1.3 Conversion
As mentioned above, in order to reduce the yield of atmospheric residue, and therefore the heavy
fuel for which demand is rapidly shrinking, it is necessary to crack the heavy molecules, in other
words to break them up into lighter molecules. The conversion is described later in this section.

1.2.2 Conversion of Heavy Ends

Because of the important part of the heavy fractions in crude oils (VGO and VR), oil industry
resorts to conversion processes. Because of the tensed energy context, with increasingly heavy
and even not-conventional crude oils (like those of Venezuela or Canada), further develop-
ments in the field of deep conversion into valuable products are still awaited. The conversion
of the heavy cuts into light cuts is carried out by various processes (Figure 1.4): thermal
12,000

Numbers in fraction
(wt % con. carbon)
10,000
Hydrocracking

8,000
Molecular weight

Heat soaking
6,000
visbreaking
Polars
21.6
4,000 Reforming

Hydrogenation
Aromatics
2,000 0.7

Saturates Hydrotreating
0.0 (remove N&S)
0
Molecular polarity

Figure 1.4
Variation of the molecular mass and the Carbon Conradson (Con. Carbon)
according to conversion processes [Andersen et al., 2001].
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 11

conversion (e.g. visbreaking or coking), catalytic without hydrogen contribution (e.g. Fluid
Catalytic Cracking or FCC) and catalytic with hydrogen contribution (e.g. hydrocracking).

1.2.3 Visbreaking and Thermal Cracking

Visbreaking is the simplest cracking process and one of the most widely used around the
world. This is because it can convert a small fraction of the atmospheric or vacuum residue
to products of the gas, gasoline and Diesel oil type. These products are low-quality because
they are rich in olefins, and therefore unstable, and rich in sulphur and nitrogen. In fact, vis-
breaking, as its name suggests, is mainly used to reduce the viscosity of the treated residue
to produce an industrial heavy fuel or bunker oil. In a more specialised form known as ther-
mal cracking of vacuum distillate, this type of process can be used to convert part of the
feedstock into lighter products of the heating fuel type, but here again the conversion is
moderate and the product quality is very mediocre. It should be noted that the distillate of
visbreaking is sometimes employed like charges for catalytic cracking FCC.

1.2.4 Coking

Coking is a thermal process of cracking at high temperature (approximately 500°C during

several hours). The vacuum residues are thus transformed deeply into solid coke with an
important output. Coking produces coke of high quality (electronic grade) or coke of lower
quality (combustion grade). The liquid effluents of coking, e.g. heavy coker gas oil
(HCGO), must undergo a hydrotreating because they are very rich in aromatic and olefinic
compounds and strongly polluted by sulphur and nitrogen.

1.2.5 Fluid Catalytic Cracking

Fluid Catalytic Cracking (FCC) is a key process for the production of gasoline or naphtha
cuts (just like catalytic reforming and isomerisation) and – to a lesser extent – of Diesel fuel.
Very flexible process, it treats feedstocks such as VGO resulting from direct distillation,
visbreaking or coking, but also hydrotreated VR having a low content of metals. The pur-
pose of the transformations are to reduce the number of atoms per molecule. The operation
is carried out in gas phase, with low pressure and temperatures ranging between 500 and
540°C. The products of conversion of catalytic cracking are mainly olefinic for the light and
strongly aromatic fractions for the heavy fractions, with an important gas yield. The
preliminary use of hydrotreating stage makes possible to obtain products of better quality,
reducing the sulphur and nitrogen content in the final products. The pretreatment of the feed-
stock prior to FCC increases also the gasoline yield and the catalytic activity of FCC.

1.2.6 Hydrocracking

Hydrocracking (HCK) is the process of reference for the production of kerosenes and Diesel
fuels. This process is particularly expensive but it produces fuels of great quality with a low
12 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

level of production of gas. It enables to treat the heavy cuts 370+°C free from asphaltenes:
VGO of direct distillation or coming from a conversion process (visbreaking, coking, FCC,
deasphalted oils, etc.). The goal of this process is to convert a broad range of heavy com-
pounds (e.g. boiling point > 370°C) into smaller molecules of weaker range of boiling point
(e.g. boiling point < 370°C). This process proceeds in two associated or separate stages
(Figure 1.5): the hydrotreating and hydrocracking stages. Essential process prior to the
hydrocracking stage, hydrotreating (HDT) aims at to eliminate impurities and to start hydro-
genation of unsaturated species (mainly aromatic compounds). The hydrotreating thus
ensures the elimination of the impurities through various reactions: hydrodesulphurisation
(HDS), hydrodeazotation (HDN) and hydrogenation of aromatic (HDA).

Pretreating Hydrocracking
section section
FG + LPG (C1-C4)
Feed

Naphtha (C8)

NiMo/Al2O3 Kerosene (C12)

NiMo/
Al2O3 + USY
NiW/SiAl
Diesel (C16)

Residue

HDS Single-stage
Full conversion

HDN
NiMo or Pt/HY

HDA
2-stages
HCK Full conversion

Figure 1.5
Schematic diagram of an HCK process, showing the HDT and HCK sections.

The hydrotreating thus effectively reduces the content of sulphur and nitrogen, under
strong hydrogen pressure and at high temperature. The HDS constitutes in particular an
essential operation of pretreatment prior to HCK stage to prevent acid HCK catalysts from
the effects of poisoning. Those HCK acid catalysts are indeed very sensitive to the presence
of basic nitrogen compounds which may adsorb and which decrease their reactivity. To
avoid this phenomenon, the nitrogen content in the feedstock treated by HCK must be low
enough, typically lower than 10 mg/kg.
The formulation of HDT catalysts is generally ensured by a transition metal sulphide
catalyst, composed by a combination of group VI metal such as molybdenum or tungsten with
a group VIII promoter like Cobalt or Nickel, supported on a oxide binder such as alumina.
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 13

The conversion by HCK itself is carried out in the second time with a bifunctional cata-
lyst combining acid function with hydro/dehydrogenation function or “metal” function. A
general formulation is based on zeolite incorporated in an alumina binder and NiMoS or
NiWS as typical transition metal sulphide active phase. This stage implies reactions of
hydroisomerisation and hydroconversion.
In line with market demand, two main processes have been developed (Figure 1.5):
– a process without intermediate separation, called a once-through or single-stage process,
– a process with intermediate separation, called a two-stage process.
Hydrocrackers were initially developed to use the two-stage process, and most of them still
use this process in the United States. The aim of this process is to produce a maximum quantity
of naphthas. The unit includes two reactors with intermediate separation of the products.
In the first reactor, conventional hydrotreatment catalysts are used, such as sulphide cata-
lysts of the NiMoS or NiWS type, supported on Al2O3 and/or on a weakly acidic support. These
catalysts can eliminate sulphur, nitrogen and oxygenated compounds (in the form of H2S, NH3
and H2O) and hydrogenate the aromatics, and also enable hydrocracking to be started if an acid
support is used. The H2, H2S, NH3, C1 and C2 gases are sent to a gas washing unit, while the
liquid products are fractionated. The tail fraction, composed of feedstock which has been
hydrotreated but not converted, is sent to the second reactor where the HCK takes place. The
conversion in this second reactor is 50% to 90%, and after separation the unconverted fraction is
recycled to obtain a higher conversion rate. The once-through or single-stage process has
mainly been developed outside the United States, with the aim of producing Middle Distillates
(MD), and it requires fewer subsequent cracking stages than gasoline production.
It differs from the two-stage process in that the hydrogen sulphide and ammonia are not
eliminated between the two operations, and the hydrotreatment step is immediately followed
by the hydroconversion step. This process exists in various forms. The two stages may take
place in sequence in a single reactor in which the catalytic beds are superimposed, or in two
different reactors. One of the major benefits of the hydrocracking process is the flexibility
that it can offer by using these different modes and configurations.
There is a degree of flexibility in the configuration of the process to be used, as well as in
the catalysts used. This means that there is a wide range of feedstocks and products.
Finally, another HCK process, called moderate or mild HCK, is derived from the single-
reactor once-through process. However, this takes place at a lower partial pressure of hydro-
gen, in the range from 40 to 80 bar, and often with lower hydrogen/feedstock ratios. These
two processes are compared in the next section, together with the positioning of HCK in
relation to the FCC process.

1.2.7 From Future Trends for Refining to New Challenges in Molecular Analysis

1.2.7.1 Trends for Refining

Despite the economic crisis in 2008, industry analysts still forecast a long-term growth in
fuel demand. The growth of the demand will be driven mainly by the needs of emerging
14 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

nations, such as China and India, and by increasing energy consumption to meet growing
domestic needs for transportation fuels. For many years, significant growth demand for fuels
was observed, while the share of heavy oils decreased in the refinery product range at world
level. It is estimated that fuel demand will grow by 44% in non-OECD countries up to 2030;
China is alleged to account for more than 43% of the increase in non-OECD demand for the
products [Worldwide Refinery Processing Review, 3Q2011].
Among motor fuels, road Diesel and kerosene will show the highest growth rates. Indeed,
despite the present economic crisis, demand for Diesel fuels is forecast to increase through
2020, albeit at a slower rate. Various forecasts indicate that the world demand for Diesel fuels
should reach about 28.2 million bpd (28.2 MMbpd) by 2020 as compared to the present demand
of 24.3 MMbpd. It is also expected that the gap between demand for Diesel and gasoline, which
was 2.6 MMbpd during 2008, will double to approximately 5 MMbpd by 2020. Although off-
road Diesel (used for heating, inland waterways or tractors and locomotives) is expected to
show a slow growth rate, on-road Diesel should increase by 1.8% annually through 2020.
Worldwide consumption of on-road Diesel is essentially due to freight movements by trucks
[Morel F et al., 2009]. Figure 1.6 shows comparative product breakdowns for 2009 and 2020.

100%
14.8% 14.7% Others
80% 8.1% 8.2% LPG
6.0% 7.1% Naphtha

60% 25.2% 23.9% Motor gasoline

40% 5.7% 6.3% Jet kerosene

15.5% 17.7% On-road Diesel
20% 13.3% 12.9% Off-road Diesel
11.3% 9.2% Fuel oil
0%
2009 2020
84.4 Mbdoe 91.3 Mbdoe

Figure 1.6
Comparison of market requirements in 2009 and 2020 according to cuts pro-
duced (LPG: liquefied petroleum gas; others: heavy fractions such as
bitumen, etc.) (Sources: adapted from Axens 2009, AIE 2010).

Consequently, gasoline and Diesel desulphurisation will continue to be the drivers of

hydroprocessing technology over the next decades.
In view of this increased demand for medium distillates, the compositions of the main
crude oils show a major imbalance in light cuts (gasoline) and medium cuts (Diesel, kero-
sene), as shown in Figure 1.7, which shows the comparative volume distribution of cuts
according to the origin of the crudes, in comparison with the demand for 2009.
Refiners will continue to adapt their operation to come with answers to the issues of
making more environmentally friendly products and more distillates while starting with
heavier and even sour crudes and reducing their overall emissions.
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 15

Demand Sahara Brent Arabian Safaniyah Boscan

(World)
crude oil (North Sea)
light light heavy crude
(Algeria) (Saudi Arabia) (Saudi Arabia) (Venezuela)
0
Gas

20 Gasolines

40
(%)

Intermediate
60
products

80
Heavy
products
100

Figure 1.7
Comparison between the demand and the composition of different crude oils:
light: LPG (C3, C4) + naphtha + gasoline; medium: kerosene + Diesel + domestic
fuel oil; heavy: heavy fuel + bitumen + base oils.

The evolution toward lower and cleaner heavy fuels, cleaner transportation fuels with more
Diesel oil and a heavier average crude supply will need more refineries which should include:
– conversion of the bottom of the barrel with resid hydrotreating and resid catalytic
cracking,
– production of middle distillates with hydrocracking,
– any unit to upgrade gasoline and diesels cuts.
The investments could be huge and operating costs also be very important to satisfy
future markets.
Catalysts and refining processes improvements have had a major impact on refining,
mainly hydrotreating, in the last ten years. The industry is awaiting others. HDT/HCK need
new catalysts with increased activity mainly for heavy cuts and deep desulphurisation of
Diesel oil. Selectivity of HDT catalyst should be increased in order to limit hydrogen con-
sumption, via better knowledge of the active sites and efficient control of their generation.
Processes integration and optimisation are another important means to get the best out of
catalysts. Optimal loading and association can only be obtained by a deep knowledge of the
kinetics of the reactions and their well-mastered modeling.
The development of analytical methods capable of improving the detailed molecular
characterisation of complex samples such as feedstocks and products is thus a critical step to
meet the last challenges.

1.2.7.2 Challenges in Molecular Analysis

To magnify the detailed composition of the petroleum oil or related products is essential for
the improvement in refinery industry in order:
16 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

– to understand the catalytic mechanisms governing their transformation,

– to design the thermodynamic and kinetic models of refining or petrochemistry
processes,
– to predict their physical properties when they can be related to the molecular composi-
tion,
– to define their specifications and the means to check them.
In addition, taking into account the environmental impact of the refinery’s processes and
the implementation of the strictest regulations make molecular information essential.
To meet these requirements, separation sciences offer a crucial advantage over the global
analysis techniques, such as physical analyses (the so called petroleum analyses such as den-
sity, distillation, etc.) and the structural analyses (elemental analysis, mass spectrometry or
nuclear magnetic resonance). Indeed, separative sciences can be used to draw up the matter
and structural balances and thereby to determine the transformation pathway for each specie.
Due to the complexity of petroleum products in terms of number of compounds, volati-
lity range, chemical class and concentration, the degree of molecular information available
varies according to the oil cut considered.
Figure 1.8 shows the molecular information available according to carbon atom range at
the beginning of 2000’s. This information is drastically decreasing along the increase of car-
bon atom number. Amongst the analytical techniques, Gas Chromatography (GC) has
become the preferred molecular analysis technique for applications related to the entire
refining industry since the end of the 80s, as shown latter in this chapter, for the lightest oils
cuts (C1-C8).
Even though GC enables to provide detailed information for the lightest cuts, the need of
improving information for C8+ fraction favored the emergence of MultiDimensional Gas
Chromatographic Methods (MDGC) designed to increase the resolution of chromatographic
systems (see Section 1.7). In 1985, the studies conducted by Giddings [Giddings JC, 1987]
led to the definition of two-dimensional systems: the analytes must undergo at least two
independent separations based on different principles (dimension); the system obtained is
such that if two compounds are separated in one dimension, they will remain resolved
throughout the process (conservation of information from one dimension to another).
The objective of these highly resolving systems is not, however, to individually identify
all the compounds – the so-called detailed molecular analysis – which is sometimes unrea-
listic and often pointless due to the similarity of the physico-chemical properties of isomer
compounds, but to obtain a better characterisation of complex cuts by group type or by
group type and carbon number for heavier cuts (middle distillates, vacuum gas oil of even
residues). For those cuts, others approaches succeed in providing group type analysis (mass
spectrometry, liquid chromatography).
The following section describes the state of the art of the analytical techniques from gen-
eral point of view to access molecular characterisation of complex oil matrices. It provides
examples of application, emphasising the increasing amount of information obtained by var-
ious analytical methods. The equally increasing complexity of the analytical strategies is
correlated to the increasing amount of information.
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 17

Individual analysis

Molecular information available

GC HRGC

Groupe type @ carbon

MDGC

MDGC
Group type analysis
MS (family, etc.)
LC-MS
LC-MS
C1 C4 C8 C12 C15 C30 C60, C60+
Carbon atom number

3 75 >4.109
Number of isomer for alkane

Figure 1.8
Molecular information available according to carbon atom number (GC: Gas
Chromatography; HRGC: High Resolution GC; MDGC MultiDimensional
GC; MS: Mass Spectrometry; LC–MS Liquid Chromatography–MS).

1.3 MOLECULAR ANALYSIS AT DIFFERENT SCALES

In the last decades, chromatographic methods, particularly gas chromatography, have played
an important role in the analysis of complex samples, allowing the identification of complex
mixture up to molecular scale.
In this part, the various scale of analysis of samples from oil industry (from global to
detailed analysis) are discussed. Then, GC is introduced under the perspective of the quest
of improved separation power: the advantages of high resolution GC, the use of selective
detection technique and the drawbacks of GC are highlighted. Additional power of conven-
tional coupled-column techniques to overcome the limitations of GC is then discussed.
Finally, a discussion of the interest of GC×GC to meet the needs in enhanced molecular
analysis as required in Table 1.6 is discussed to introduce the following chapter.

1.3.1 From Global Analysis to Detailed Analysis of Petroleum Products

Analysis of complex petroleum products is essential to measure the physico-chemical pro-
perties of the finished products related to their specifications, but also to know the composi-
tion of the feedstocks and the intermediate products to gain a better understanding of the
conversion processes involved. We can identify the global characterisation methods which
18 Gas Chromatography and 2D-Gas Chromatography for Petroleum Industry

apply to all petroleum products, given a certain degree of flexibility of the implementation
conditions, and the detailed characterisation methods intended to supply molecular informa-
tion through identification of the individual constituents [Wauquier JP, 1994; Hsu CS,
2003]. This second strategy results from the need to know the detailed composition of the
hydrocarbons in order to determine the input data of the process modeling. In addition, the
macroscopic properties can be deduced by molecular characterisation, using blending laws.
Detailed analysis involves identifying and quantifying all constituents present in a petro-
leum or similar product. However, this number increases intrinsically depending on the
number of carbon atoms of the hydrocarbons contained in the product since the possibilities
of associating carbon and hydrogen atoms to form isomer compounds multiply. Obviously,
not all combinations are necessarily present, but this nevertheless gives an idea of the diver-
sity of the structures. For example, the possible number of isomers for a 5-carbon atoms
paraffin is 3, but it increases to 75 for 10 carbon atoms and over 4 billion for 30-carbon
atoms [Lefebvre G, 1978]. For the family of olefins, the number of isomers expected is even
greater due to those related to the position and to the cis-trans configuration of the double
bond. Faced with this impressive number of constituents, it is obvious that the detailed ana-
lysis will be increasingly difficult, even unrealistic, as the hydrocarbons become heavier
(greater numbers of carbon atoms and isomers).
After giving an overview of the global, elemental and structural characterisation
methods, this part describes the state of the art of these molecular analysis techniques by
family or class of compounds and by compound (“detailed” analysis), specifying their fields
of application. Lastly, their limitations are examined.

1.3.2 Global Characterisation

A certain number of test methods have been standardised by the American Society for
Testing and Materials (ASTM) and are frequently used to monitor pilot units. They concern,
for example, the viscosity index (ASTM D2270), density (ASTM D1298 or D4052) and vol-
atility. The volatility of a petroleum product is one of the most critical characteristic: it is
determined by its distillation curve, which defines the boiling point as a function of the per-
centage of material distilled by volume (or mass). Test method ASTM D86 applies to distil-
lation of most commercial products, while method ASTM D1160, distillation of petroleum
products at reduced pressure, is intended for low-volatility or thermolabile products. Prod-
ucts with a wide range of boiling points, in particular crude oils, are characterised by ASTM
D2892, the so called True Boiling Point method.

1.3.3 Elemental and Structural Analysis

The elemental and structural analysis methods are based on the interaction of matter and elec-
tromagnetic radiation. More complete information about the interest of these techniques for
petroleum samples analysis can be found in the references mentioned [Colthup NB et al.,
1990]. Elemental analysis by atomic absorption or X-ray fluorescence consists in measuring
energy level differences between electron orbitals of an atom. Based on electron transitions
 Chapter 1 • Molecular Analysis for Petroleum Products: Challenges and Future Needs 19

between energy levels of the bonds, ultraviolet (UV) spectrometry can be used to determine
the mono-, di- and poly-aromatic compounds (ASTM D2269). In infrared (IR) absorption
spectrometry, the energy differences associated with the characteristic vibration frequencies
of functional groups can be used to deduce the structural patterns and determine, for example,
the distribution by type of aromatic and paraffinic carbons. Lastly, Nuclear Magnetic Reso-
nance (NMR) concerns the transitions between the spin energy states; the structure of the
hydrocarbons can be determined by spectrum analysis according to the position, number and
intensity of the peaks. Although it offers the most complete structural characterisation, NMR
remains difficult to implement for everyday monitoring of pilot units, is expensive and rela-
tively insensitive.
The various elemental and structural characterisation techniques can therefore be used to
determine a product’s identity card and provide “average” molecular information based on
the hydrogen, carbon and heteroatom contents and the types of chemical bond. These data
can then be correlated with physico-chemical properties such as the density or cetane number.
In view of the needs for detailed characterisation of petroleum products, however, other
techniques giving the distribution by hydrocarbon chemical family and, if possible, by num-
ber of carbon atoms, must be implemented.

1.3.4 Hydrocarbon Family Analysis

1.3.4.1 Mass Spectrometry

Mass Spectrometry (MS) has become the preferred technique to obtain the distribution by
hydrocarbon family in most petroleum products [Mendez A and Bruzual J, 2003]. The
molecules introduced in the mass spectrometer are volatilised, ionised and detected accord-
ing to their mass/charge (m/z) ratio.
High energy electron ionisation (70 eV), which is widely used, leads to fragmentation of
the molecules characteristic of their chemical structure. While fragmentation may facilitate
qualitative analysis by family through their specific mass spectrum fingerprint, quantitative
analysis remains more complex since molecules of different mass may form identical frag-
ments. The less volatile the cut and the greater the diversity of the molecules and the number
of isotopes, the more critical it becomes. The intensity of an ion is then proportional to a sen-
sitivity constant and the partial pressure of the molecule in the source, i.e. to the concentration
of this molecule in the mixture. Since the mass spectrum of a petroleum product is the sum of
the mass spectra of all the molecules, we require the same number of independent equations
as there are different families, which will be solved using a coefficient matrix. This matrix is
simplified to a diagonal matrix if the spectrometer resolution increases. While high-resolution
mass spectrometers facilitate deconvolution of mass spectra and avoid fractionation by liquid
phase chromatography, which is long and can generate errors, they remain very expensive
and difficult to use, i.e. incompatible with routine analysis [Gallegos EJ et al., 1967]. Current
developments are converging towards analysis of low-volatility, heavy products requiring
soft ionisation sources. The time-of-flight analyser seems in fact to be the best to meet the fol-
lowing requirements: more sensitive and more resolving instruments.
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