Fuel 89 (2010) 2338–2345

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Improved hydrocarbons analysis of heavy petroleum fractions by high

temperature comprehensive two-dimensional gas chromatography
Thomas Dutriez a, Marion Courtiade a,*, Didier Thiébaut b, Hugues Dulot a, Marie-Claire Hennion b
a
IFP, BP3, 69360 Solaize, France
b
ESPCI, PECSA UMR CNRS 7195, 10 rue Vauquelin, 75231 Paris Cedex 05, France

a r t i c l e i n f o a b s t r a c t

Article history: Conventional comprehensive two-dimensional gas chromatography (2D-GC or GC  GC) is now widely
Received 15 September 2009 used for middle distillates analysis; only a few applications are devoted to heavy fractions such as vac-
Received in revised form 27 November 2009 uum gas oils or vacuum residues. A recent extension of GC  GC range in suitable high temperature con-
Accepted 30 November 2009
ditions allowed quantitative analysis of a full vacuum gas oil (VGO) up to nC60. Considering this study as a
Available online 16 December 2009
new breakthrough for the challenge of heavy petroleum fractions analysis, the application of high-tem-
perature two-dimensional gas chromatography (HT-2D-GC) to 12 VGOs from different origins (geo-
Keywords:
graphic and processes) and one de-asphalted oil (DAO) is described in this paper. The comparison with
High-temperature comprehensive two-
dimensional gas chromatography
standardized methods, liquid chromatography and mass spectrometry, illustrates the reliability of the
GC  GC method for heavy cuts analysis. Furthermore, quantitative distributions by chemical families could be
Hydrocarbons analysis built for the first time, which allow a better description and more relevant comparisons between heavy
Vacuum gas oils petroleum fractions. Except for heavier cuts such as DAO, this powerful technique is widely applicable on
De-asphalted oil VGO fractions. These results should increase the analytical information concerning heavy cuts and will be
helpful to understand reactions involved in petroleum processes.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction
In the next decade, continuously rising demand for fuels is
expected worldwide. To satisfy this demand and to respect more
stringent regulations, petroleum industry has to face the chal-
lenge of upgrading the heavier cuts into valuable products, like
diesel. Among efficient conversion processes for vacuum gas oil
(VGO) cuts, there are catalytic ones: fluid catalytic cracking
(FCC) and hydrocracking (HCK), which should be combined with
a pre-purification by hydrotreatment (HDT). Realized on sulfide
catalyst, the main goal of hydrotreatment is to reduce sulphur,
nitrogen content and hydrogenate aromatic compounds. Further-
more, the conversion of heavier cuts such as vacuum residues
using fixed bed or ebullated bed process gives products which
need to be severely upgraded in order to reach the fuel specifi-
cations. To improve qualitative and quantitative performances of
those processes, it is essential to optimize operating conditions
by studying the kinetics of reaction involved. Therefore, the
molecular analytical characterization of VGO is extremely impor-
tant, to determine aromatic, saturated or heteroatomic com-
pounds both in feedstock VGO and in converted products.
Characterization of VGO fractions (C20–C60) is a difficult analytical
challenge because the number of hydrocarbon isomers drastically
* Corresponding author. Tel.: +33 04 78 02 20 76.
E-mail address: marion.courtiade@ifp.fr (M. Courtiade).
increases with the number of carbon atoms. (They should contain
more than 1 million of compounds!) Current analytical methods give
a global description of VGOs based on boiling range (simulated
distillation) or on elementary and structural analysis (e.g. nuclear
magnetic resonance, X-ray fluorescence). Only liquid chromatogra-
phy (LC) and mass spectrometry (MS) allow quantitative analyses:
i.e. saturated, aromatic and resins compounds in LC and 32 families
of hydrocarbon and sulphur compounds in MS [1]. However, analyt-
ical description of VGOs remains partial. High resolution mass
spectrometry (HR/MS) with Fourier transform ion cyclotron reso-
nance MS (FT-ICR/MS) [2,3] is currently being studied as a possible
innovative method for VGOs characterization but the quantification
step remains a daunting task. To overcome the lack of molecular
description of VGOs, reconstruction algorithms, based on available
analytical data, were developed [4]: for heavy cuts a low relevance
was observed due to the limitation of quantitative methods as no-
ticed above. In order to obtain a more accurate description of VGOs,
new analytical data, combining boiling point and chemical structure
information, are needed.
For very complex samples, multidimensional comprehensive
systems are gaining importance [5]. By the combination of two
chromatographic columns with different separation mechanisms,
the overall peak capacity [6] is increased, offering a decisive advan-
tage. Many different combinations are possible: LC  LC [7,8],
LC  GC [9,10], SFC (supercritical fluid chromatography)  GC
[11], SFC  SFC [12] SFC  LC [13], LC  GC  GC [14], GC  GC  GC

0016-2361/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.11.041
 T. Dutriez et al. / Fuel 89 (2010) 2338–2345 2339

[15]. Due to simplicity and reliability, comprehensive multidimen-
sional gas chromatography (GC  GC) is, by far, the most applied
comprehensive chromatographic mode. Using a classical combina-
tion of non-polar  polar columns, the sample is submitted to two
dimensions of separation according to volatility and polarity,
respectively. GC  GC [16,17] applications are gaining ground in
food industry, biology, environment and, especially, petroleum
and petrochemistry [18]. Important developments were recently
reached in the characterization of diesel samples [19], including
nitrogen [20] and sulphur speciation [21], Fischer–Tropsch products
[22], hydrocracking products [23], biomass effluents [24] or petro-
leum biomarkers [25].
However, applications of GC  GC are currently limited to mid-
dle distillate fractions (up to boiling point of 450 °C). Temperature
limitation of polar columns and modulation problems at the
desorption step, were the most important difficulties to extend
GC  GC towards heavier compounds. A flow programming of
cryogenic N2 modulator [26,27] has recently been shown to im-
prove desorption of heavier compounds and to provide better peak
shapes; GC  GC separation of a partial VGO up to nC47 was re-
ported [27]. In a recent publication [28], our group has recently
showed an extension of comprehensive multidimensional gas
chromatography range up to nC60, by choosing high temperature
conditions and adapting modulation step. For the first time, new
conditions allowed an extension of GC  GC application range to
high temperature conditions for a quantitative application of a
whole VGO.
In this paper, the same high-temperature two-dimensional gas
chromatography (HT-2D-GC) conditions were applied to 12 VGOs
and one De-asphalted oil (DAO) in order to check the applicability
of this method to a wide range of heavy cuts, to determine the lim-
itations and to confirm HT-2D-GC as a new powerful way to analyze
VGOs. HT-2D-GC quantitative results were compared to those of
usual methods, liquid chromatography and mass spectrometry.
From new data combining boiling point and chemical structure, a
comparison of the composition of studied VGOs was conducted.
2. Experimental
2.1. HT-2D-GC experiments
All experiments were carried out using a 2D chromatograph
(Trace GC, Thermo, Italy) equipped with a CO2 dual jets modulator,
a split injector at 360 °C (1/100) (0.2 ll) and a flame ionization detec-
tion (FID) system (370 °C, 100 Hz). H2, air, He (make-up) flows were
respectively 35, 400 and 35 mL/min. Analytical gases were provided
by Air Liquid (Feyzin, France) at a minimum purity of 99.99%. Helium
was used as a carrier gas at constant flow rate. The column set
consisted of a combination of a non-polar first column (DB1-HT, dim-
ethylpoly-siloxane, J&WScientific, 10 m  0.32 mm, 0.1 lm) and a
mid-polar second column (BPX-50, (50%phenyl)polysilphenylene-
siloxane, SGE, 1 m  0.1 mm, 0.1 lm), placed in the same oven. The
GC system was operated in programmed temperature conditions
from 100 °C to the maximum temperature of column set (BPX-50:
370 °C) at 2 °C/min. The system was operated under constant flow
close to the optimum velocity of the first column [29]. 2D modula-
tion, provided by dual stage carbon dioxide jets, was carried out at
the beginning of the second column. The temperature of cryogenic
jets was set at 40 °C (in room temperature conditions) by adjusting
the inner diameter of restrictors used for CO2 expansion. The modu-
lation period was set to 20 s.
2.2. Standard analysis of VGO
The high-temperature simulated distillation (adapted from ASTM
D2887) was performed at constant helium flow of 10 mL/min, using
a HP 6890 gas chromatograph (Agilent Technologies, Massy, France)
equipped with a FID (400 °C) and a cool on-column injector. A metal-
lic capillary column MXT-1 (Restek, France) SilcosteelÒ-treated
stainless (10 m  0.53 mm  0.5 lm) was heated from 35 °C to
390 °C at 10 °C/min. A simulated distillation curve was obtained
using ChromDis software (Gecil Process, France). Preparative liquid
chromatography was performed under normal phase conditions
using a column filled with silica and alumina. Three fractions were
collected increasing the mobile phase eluting power: saturated com-
pounds, aromatic compounds and resins fraction. The mass spectro-
metric analysis were derived from Fisher method [1,30], by using a
mass spectrometer (Autoconcept, MSI, United Kingdom) equipped
with a magnetic sector. After the removal of the resins fraction by
LC, samples were ionized by electronic ionization at 70 eV. A mass
spectrometric resolution of 10,000 allowed the separation of multi-
plets and identical mass rating. The quantification of each hydrocar-
bon family was performed using a correlation matrix based on an
average carbon atoms number.
2.3. Samples and chemicals
Solvents of HPLC grade were purchased from Sigma–Aldrich (St.
Quentin Fallavier, France). For an easy identification of 2D elution
zones, a synthetic test mixture of hydrocarbons (n-alkanes,

Table 1
Origin, physical characteristics and elementary composition of VGOs and DAO studied by HT-2D-GC.

Sample Process Geographic Density at 15 °C (g/ Total sulphur (% Total nitrogen Boiling point interval
origin cm)a S)b (ppm N)c (°C)d
VGO A Straight run distillation Middle-east 0.9282 2.03 1527 376–554
VGO B Straight run distillation Middle-east 0.9414 2.92 1357 399–582
VGO C Straight run distillation Chinese 0.8808 0.13 830 380–566
VGO D Straight run distillation Africa 0.9429 0.42 1655 358–550
VGO E Straight run distillation Venezuela 0.9811 3.44 2667 375–545
VGO F Mixture straight-run VGOs Middle-east 0.9237 2.41 836 366–533
VGO G Mixture of gasoil, VGOs and desaphalted – 0.9611 2.55 1580 362–705
oils
VGO H Hydrotreatment vacuum residue Iraq 0.9341 0.38 1805 355–543
VGO I Vacuum residue hydrotreatment Middle-east 0.9531 1.31 1717 403–547
VGO J Vacuum residue hydrotreatment _ 0.9547 0.58 3765 357–522
VGOK Vacuum residue hydrocracking Pilaon 0.9425 0.46 1450 301–416
VGO L Vacuum residue hydrocracking Middle-east 0.8646 8 ppm 2 375–521
DAO Desaphalted oils Safanya 0.9450 – – 466–710
a
Determined by NF ISO12185.
b
Determined by NF ISO14596 or ISO20884.
c
Determined by NF 07058 or ASTM D4629.
d
Determined by HT-SimDist (ASTM D2887) (5–95% weight).
2340 T. Dutriez et al. / Fuel 89 (2010) 2338–2345

naphthenes, monoaromatics and polyaromatics [28]) (Sigma–Al- 2.4. Data treatment

drich, France and Alfa Aesar, France) within the VGOs boiling point
range, was prepared in CS2 (800–1000 mg/kg), and used in HT-2D-
GC conditions.
Petroleum samples (VGOs and DAO), from various geographic
origins, separation or catalytic processes, were supplied by IFP-
Lyon (Table 1). After heating for 10 min at 80 °C, a dilution at 1/5
in CS2 allowed the complete dissolution of samples.
Raw data of FID signals were acquired using Polycard software
(Thermo, Italy) and exported as a CSV-file for further data processing.
GC  GC contour plotting, retention time measurement, blob fitting
and peak integration were performed by using 2DChromÒ (Thermo,
Italy). Intensities were visualized via contrasting colors, ranging from
pale blue to dark blue respectively for minor and major peaks.

Fig. 1. HT-2D-GC contour plots of five VGOs and one DAO (S: saturates, 1A: monoaromatics, 2A: diaromatics, 3A: triaromatics; 4A +: tetraaromatics +). Conditions as in
Section 2.1.

3. Results and discussion
3.1. HT-2D-GC conditions
As described previously [28], the extension of GC  GC applica-
tion range to heavier matrixes could be obtained by choosing
adapted conditions in order to lower the elution temperatures of
solutes: wide bore first column with high phase ratio (1b = 800),
very short secondary column (2L = 0.5 m) and high temperature
conditions. Lowering elution temperatures induces high peak
broadening of most aromatic compounds: this implies to adapte
temperature conditions of cryogenic modulation (CO2 jets) and to
choose a high modulation period (20 s) to keep a sufficient resolu-
tion between solutes.
3.2. Application of HT-2D-GC to various VGOs
HT-2D-GC conditions were applied for each petroleum sample
described in Table 1. 2D contour plots of the six of them were com-
piled in Fig. 1. 2D elution zones were determined using the test
mixture. Dotted lines separate saturated compounds and aromat-
ics by number of rings.
3.2.1. Qualitative analysis
A simple visual observation of 2D contour plots, allowed differ-
ences of composition to be clearly identified by the variation of
intensity. Due to the high number of compounds in VGO matrixes,
the resolution in second dimension was quite relatively poor, espe-
cially between saturates and monoaromatics. This was even more
the case for compounds eluting at high first dimension retention
times, for example VGO I, due to a lack of second dimension selec-
tivity in higher temperature conditions. This is even more marked
for DAO sample as the distinction between chemical families could
not be seen. Concerning the DAO sample, which is known to be
composed by heaviest compounds of crude oil excepted asphal-
tens, not all compounds are eluted from 2D system. As a result,
application possibilities of HT-2D-GC appear to be dedicated to
matrixes composed by semi-volatile compounds such as VGO,
rather than DAO or vacuum residue, composed by non-volatile
ones.
3.2.2. Quantitative analysis
To evaluate the sample recovery for each matrix, distributions
by boiling point and simulated distillation curves were plotted
from HT-2D-GC results. Simulated distillation curves by HT-2D-
GC are obtained by dividing each 2D elution zone into slices of first
dimension. The retention time of each slice was converted into a
VGO A
VGO B
700
VGO C
VGO D
VGO E
VGO F
600 VGO G
By HT-2D-GC (°C)
VGO H
VGO I
VGO J
500 VGO K
VGO L
DAO
--- +/-10°C
400
300
300 350
Fig. 2. Comparison between cumulated weight% (w/w) obtained by HT-2D-GC and HT-SimDist for 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%.
T. Dutriez et al. / Fuel 89 (2010) 2338–2345 2341
boiling point using an established relationship between retention
times and boiling points of n-alkanes. The area of each slice was
converted into a cumulated weight% (w/w) to give a distillation
curve. Due to the use of split inlet, HT-2D-GC system induced dis-
crimination towards heavier compounds. Therefore, a correction
factor was established from test mixture to correct all quantitative
results.
Cumulated weight% (w/w) obtained from HT-2D-GC and refer-
ence methods (HT-SimDist) were compared in a parity diagram
(Fig. 2). For almost all VGOs, distillation curves obtained by HT-
2D-GC were close to those of reference. For matrixes having a final
boiling point (corresponding to 95% distillated) higher than 600 °C
(VGO G, DAO), distillation curves by HT-2D-GC were under esti-
mated, owing to a lack of elution for very heavy compounds, which
means a partial sample recovery. Therefore, HT-2D-GC conditions
allowed to elute all heavy petroleum matrixes having a final boil-
ing point (95% distillated) not higher than 600 °C, which corre-
sponds to almost all VGOs. As the sample recovery, first step of
quantitative analysis, was suited for VGOs analysis, an accurate
quantification by chemical family was carried out.
In order to carry out quantitative analysis by chemical group,
the identification of 2D elution zones was checked using the test
mixture; the distinction between zones were defined as the lowest
value of intensity between valleys. The quantification step of iden-
tified VGO families (saturates, monoaromatics, diaromatics, triaro-
matics, and tetraaromatics +) was carried out by normalizing the
full 2D contour plot area to 100% and taking into account the dis-
crimination of the system towards heavier compounds.
Sulphur aromatic compounds which correspond approximately
to 20% (w/w) of straight-run VGOs, supposed to be eluted in the
same zones of aromatic hydrocarbons in 2D contour plots. Table
2 gathers results of quantitative analysis by chemical group by
HT-2D-GC for all petroleum samples. For DAO sample, group-type
quantification was only estimated on eluted compounds. Confi-
dence intervals were determined for each group by three repeti-
tions analysis on VGO F.
For all petroleum samples, analysis by reference quantitative
methods (LC and MS Fischer) were also carried out; results are re-
ported in Table 3.
In order to compare the overall HT-2D-GC results of with those
of reference methods, parity diagrams were built. The comparison
of HT-2D-GC quantitative results towards LC ones is presented in
Fig. 3. Resins fraction was considered as composed by the most
aromatic and polar compounds in tetraaromatics elution zone in
2D contour plots. For almost all VGO, a good overall agreement
was obtained between distributions of aromatic + resins and satu-
rated compounds, showing that our 2D system provided reliable
separation by aromatic structures. Nevertheless, some differences
400 450 500 550 600 650 700
By HT-SimDist (°C)
2342 T. Dutriez et al. / Fuel 89 (2010) 2338–2345

Table 2
Group-type quantification of petroleum samples by HT-2D-GC.

Samples HT-2D-GCa
Saturates Monoaromatics Diaromatics Triaromatics Tetraaromatics +
VGO A 45.9 15.9 13.3 10.6 14.3
VGO B 37.8 15.3 16.4 12.6 17.9
VGO C 63.9 14.0 9.7 5.4 7.0
VGO D 36.7 17.4 17.9 10.1 17.8
VGO E 17.0 23.2 26.0 19.6 14.2
VGO F 47.8 (±2.2) 15.1 (±1.1) 14.8 (±0.6) 10.6 (±0.5) 11.8 (±0.7)
VGO G 38.5 15.5 15.5 12.7 17.8
VGO H 38.8 21.7 15.9 11.3 12.3
VGO I 19.7 21.6 20.7 16.1 21.9
VGO J 31.8 18.8 15.2 14.2 20.0
VGO K 33.3 25.8 20.0 13.4 7.5
VGO L 78.4 13.4 3.1 1.7 3.4
DAO 26.3 14.7 19.9 14.8 24.3
a
Confidence interval determined on VGO F are reported in brackets.

Table 3
Group-type quantification of petroleum samples by LC and MS Fischer.

Samples LCa MSb

Saturates Aromatics Resins Saturates Monoaromatics Diaromatics Triaromatics Tetraaromatics +
VGO A 47.7 43.3 8.0 50.6 12.1 13.9 9.4 14.0
VGO B 37.4 52.7 9.6 44.7 10.9 14.3 10.9 19.2
VGO C 71.3 22.3 5.7 73.2 10.5 7.7 4.1 4.5
VGO D 49.7 40.4 9.3 42.5 17.1 11.4 6.9 22.1
VGO E 26.1 59.8 12.3 27.4 13.3 22.9 15.6 20.8
VGO F 47.5 47.0 5.8 50.0 11.4 13.9 11.2 13.5
VGO G 31.5 56.8 10.3 35.3 9.2 14.3 14.7 26.5
VGO H 41.4 50.7 7.5 41.3 19.3 14.4 9.2 15.8
VGO I 25.7 65.2 9.1 25.7 22.7 15.1 14.7 21.8
VGO J 38.5 48.4 12.4 39.9 16.2 13.5 13.6 16.8
VGO K 46.9 43.5 4.8 49.3 17.0 25.0 6.2 2.5
VGO L 88.0 11.3 0.7 85.0 9.5 3.0 1.1 1.4
DAO 26.3 62.6 9.5 n.d. n.d. n.d. n.d. n.d.
a
LC method repeatability, CI (confidence interval) = 0.011  C.
b
MS method repeatability, if 0 < C < 20%, CI = 0.009  C + 0.4; if C > 20%, CI = 0.022  C.

could be observed in HT-2D-GC: aromatics + resins are overall
overestimated, while saturates are underestimated, probably due
to the difficult distinction between saturates and monoaromatics
compounds in HT-2D-GC, especially for naphthenic solutes. This
is actually the case for VGO L, coming from hydrotreatment pro-
cess, which should contain high proportion of saturates. High vari-
ations were also observed for VGO D, supposed to be composed by
high content of polynaphthenes. For VGO K, a lower boiling range
than others could induce variations for the application of integra-
tion masks.
The comparison of HT-2D-GC quantitative results with those of
MS Fischer method was performed and is shown in Fig. 4. Compar-
ison was done keeping in mind that Fischer method results do not
take into account resins compounds. Therefore, MS quantitative re-
sults are anyway biased, especially for polyaromatics compounds,
which should mainly contain resins.

Saturates
Aromatics + Resins
80 --- +/- 10% D
70
K
By HT-2D-GC (% w/w)

60
50
L
40
30
20
10
0
0 20 40 60 80
By LC (% w/w)

Fig. 3. Comparison of quantitative results by HT-2D-GC and LC separation. Samples presenting high variations are noticed.
 T. Dutriez et al. / Fuel 89 (2010) 2338–2345 2343

Monoaromatics Triaromatics
Diaromatics Tetraaromatics +
25 D 25
--- +/- 10%
--- +/- 10%

By HT-2D-GC (% w/w)
By HT-2D-GC (% w/w)

20 20
K
15 15 K
K D
10 10

5 5

0 0
0 5 10 15 20 25 0 5 10 15 20 25

By MS (% w/w) By MS (% w/w)

Fig. 4. Comparison of quantitative results by HT-2D-GC and MS Fischer. Samples presenting high variations are noticed.

Sulphur aromatic families, which are distinguished in MS meth-
od, were gathered with quantitative results of aromatic hydrocar-
bons to facilitate the comparison with HT-2D-GC results. It should
be noted that anyway, the most of sulphur compounds are con-
tained in the resins fractions and therefore not taken in account
with MS.
Quantitative results between families followed almost the same
profile for both analytical methods. However, some low variations
could be observed as previously for VGOs K, D and also G. Three
reasons could explain these differences: mass spectrometric reso-
lution of Fischer method is not enough good to obtain exact mass,
inducing interferences between chemical group-types. On the
other hand, as previously mentioned, the resolution of second
dimension, for HT-2D-GC technique, is not high enough to obtain
a perfect separation, implying some coelutions between chemical
families. Lastly, MS Fischer results not take into account analytes
in resins fractions, as nitrogen or sulphur aromatic compounds,
what could also explain some differences in parity diagrams.
3.2.3. Distribution by chemical family
HT-2D-GC analysis of VGO allowed to compete with reference
analytical methods for group-type quantification: for the first time,
in one analysis, information according the boiling point and the
chemical structure were obtained for heavy fractions. As for mid-
distillates, data could be represented by distillation or distribution
curves by chemical family. Fig. 5 compiles those distributions for
three VGOs and the DAO. After an assignment of 2D elution zones
to chemical structure, quantification was realized for each group

1.8 0.9
1.6 VGO C Saturates VGO F
0.8
Monoaromatics
1.4 Diaromatics 0.7
Triaromatics
1.2 0.6
Tetraaromatics+
% W/W

% W/W

1 0.5
0.8 0.4
0.6 0.3
0.4 0.2
0.2 0.1
0 0
250 350 450 550 650 250 350 450 550 650
Temperature (°C) Temperature (°C)

0.5 0.25

VGO J DAO
0.4 0.2

0.3 0.15
% W/W
% W/W

0.2 0.1

0.1 0.05

0 0
250 350 450 550 650 250 350 450 550 650
Temperature (°C) Temperature (°C)

Fig. 5. Chemical distributions by group-type of four petroleum samples.

2344 T. Dutriez et al. / Fuel 89 (2010) 2338–2345

20 same proportion of each chemical group. The lack of information

VGO B
18 VGO C
for end of distributions confirmed that HT-2D-GC method is not ut-
16 VGO D terly adapted for this kind of sample, due to elution problems for
14
VGO H
heaviest compounds.
VGO J
12 VGO L To compare each VGO, boiling point distributions for saturates
% W/W

10
8
6
4
2
0 of temperature was observed; this is related to the reactions in-
260 310 360 410 460 510 560 610
Temperature (°C)
Fig. 6. Plots of boiling point distributions for saturates of six VGOs.
and for each slice of modulation period (20 s). Boiling point of each
slice was obtained from reference n-alkanes data analysis in order
to compare to simulated distillation (ASTM D2887). Calibration of
simulated distillations built with each hydrocarbon families may
be closer to the physical distillation. The chosen step (0.7 °C corre-
sponding to 20 s) allows to represent precisely the variations of
each family according to the temperature. For saturates, n-alkanes
are clearly remarkable from the rest of matrix, due to a high
proportion.
For the four samples, various distribution shapes were obtained:
for VGO C pseudo-Gaussian distributions classically described
straight-run VGOs. For VGO F, a bimodal distribution revealed the ori-
gin from a mixture of VGOs. For VGO J, a high proportion of triaromat-
ic compounds was observed due to the nature of process involved
(vacuum residue hydrocracking). For DAO, Gaussian shapes centred
in higher temperatures than VGO ones were observed in almost the
and aromatic groups (Figs. 6 and 7) were constructed for six VGOs.
For those diagrams, a step of 25 °C was chosen to smooth the curves.
Concerning saturates (Fig. 6), almost the same pseudo-Gaussian
curves were obtained for VGOs B, C, D, H and J, differences being
due to variations of median temperature or quantity in cuts
(VGO C). For VGO L, a high proportion of saturates in lower range
660
volved in hydrotreatment process leading to a high conversion of
aromatic rings into naphthenes, associated to a low hydrocracking.
The comparison of aromatic distributions according to the
boiling point (Fig. 7) highlights the differences of composition.
Especially for VGO J, it can be noticed, a high proportion of triaro-
matics and tetraaromatics + in low temperature range compared
to the others samples. This could be clearly observed in 2D con-
tour plots showing in Fig. 1, and should correspond to uncon-
verted compounds after vacuum residue hydroconversion.
Interessently, for VGO D, a high proportion of monoaromatic
and diaromatic compounds was observed between 400 and
500 °C. They could be aromatic biomarkers or coeluted polynaph-
thens. For VGO L, distributions confirmed the low proportion of
polyaromatic compounds after hydrotreatment.
4. Conclusion
Newly developed conditions [28] of HT-2D-GC were applied on
twelve VGO samples; they confirmed application possibilities of
HT-2D-GC analysis to heavier samples than gas oils. Using

4.5 6.0
Monoaromatics VGO B Diaromatics
4.0 VGO C
VGO D
5.0
3.5 VGO H
VGO J
3.0 4.0
VGO L
% W/W

2.5
% W/W

3.0
2.0

1.5 2.0

1.0
1.0
0.5

0.0 0.0
260 310 360 410 460 510 560 610 660 260 310 360 410 460 510 560 610 660
Temperature (°C) Temperature (°C)

3.0 4.5
Triaromatics Tetraaromatics +
4.0
2.5
3.5

2.0 3.0
% W/W

2.5
% W/W

1.5
2.0

1.0 1.5
1.0
0.5
0.5

0.0 0.0
260 310 360 410 460 510 560 610 660 260 310 360 410 460 510 560 610 660

Temperature (°C) Temperature (°C)

Fig. 7. Plots of boiling point distributions for aromatic groups of six VGOs.
 T. Dutriez et al. / Fuel 89 (2010) 2338–2345 2345

HT-2D-GC allowed to demonstrate that new quantitative reparti- References

tions by boiling point and by chemical group-type could be obtained
for heavy cuts. Their compares gave an unsurpassed quantitative [1] Fafet A, Bonnard J, Prigent F. Oil Gas Sci Technol 1999;54:453.
[2] Stanford LA, Kim S, Rodgers RP, Marshall AG. Energy Fuels 2006;20:1664.
description of variations, in term of chemical composition of VGOs, [3] Al-Hajji AA, Muller H, Koseoglu OR. Oil Gas Sci Technol 2008;63:115.
on the whole range of boiling point. Nevertheless, it seems that con- [4] Verstraele JJ, Revellin N, Dulot H, Hudebine D. Abstr Pap Am Chem Soc
ditions used for HT-2D-GC are limited to VGO samples, as heavier 2004;227:U1070.
[5] Bartle KD, Mondello L, Lewis AC. Multidimensional chromatography. Chischester:
samples (DAO) are not utterly eluted. We think that we approached Wiley; 2001.
the elution limits for the use of GC  GC technology. It seems that the [6] Giddings JC. J High Resolut Chromatogr 1987;10:319.
extension of GC  GC towards heavy cuts could not be done as long [7] Guiochon G, Marchetti N, Mriziq K, Shalliker RA. J Chromatogr A
2008;1189:109.
as the stability at high temperature of stationary phases is not im-
[8] Dugo P, Cacciola F, Kumm T, Dugo G, Mondello L. J Chromatogr A
proved. Due to the complexity of such heavy matrixes, additional 2008;1184:353.
dimensions should extend even more the knowing of heavy cuts, [9] Edam R, Blomberg J, Janssen HG, Schoenmakers PJ. J Chromatogr A
such as specific detector or the implementation of 3D techniques, 2005;1086:12.
[10] de Koning S, Janssen HG, van Deursen M, Brinkman UAT. J Sep Sci
as really shown for mid-distillates analysis. 2004;27:397.
At once, these new results for heavy cuts appear to be helpful [11] Venter A, Rohwer ER. Anal Chem 2004;76:3699.
to optimize petroleum conversion processes. Actually, kinetic [12] Lavison G, Bertoncini F, Thiébaut D, Beziau JF, Carraze B, Valette P, et al. J
Chromatogr A 2007;1161:300.
modelling of various processes is based on molar content of [13] Francois I, Pereira AS, Lynen F, Sandra P. J Sep Sci 2008;31:3473.
chemical structure, which could not be afforded by current ana- [14] J. Blomberg. Presented at 5nd GC  GC symposium, Riva Del Garda, conference
lytical methods, especially by mass spectrometric ones. From PLe.01; 26–30 May 2008.
[15] Watson NE, Siegler WC, Hoggard JC, Synovec RE. Anal Chem 2007;79:8270.
quantitative distributions by HT-2D-GC, new quantitative reparti- [16] Dalluge J, Beens J, Brinkman UAT. J Chromatogr A 2003;1000:69.
tions of molecules in terms of molar content could be obtained by [17] Adahchour M, Beens J, Brinkman UAT. J Chromatogr A 2008;1186:67.
converting ebullition temperatures into carbon atoms number. [18] Blomberg J, Schoenmakers PJ, Brinkman UAT. J Chromatogr A 2002;972:137.
[19] Adam F, Bertoncini F, Thiébaut D, Esnault S, Espinat D, Hennion MC. J
Therefore, HT-2D-GC method should allow to validate molecular Chromatogr Sci 2007;45:643.
reconstruction mechanisms, and also to study kinetic modelling [20] Adam F, Bertoncini F, Brodusch N, Durand E, Thiébaut D, Espinat D, et al. J
of the various hydrotreatment process of VGOs, based on chemi- Chromatogr A 2007;1148:55.
[21] Ruiz-Guerrero R, Vendeuvre C, Thiébaut D, Bertoncini F, Espinat D. J
cal structure instead of ebullition temperature. The information
Chromatogr Sci 2006;44:566.
obtained by HT-2D-GC could also be implemented directly to [22] Vendeuvre C, Bertoncini F, Duval L, Duplan JL, Thiébaut D, Hennion MC. J
build kinetic models of conversion processes without the use of Chromatogr A 2004;1056:155.
prior models of molecular reconstruction, which positions [23] Hamilton JF, Lewis AC, Millan M, Bartle KD, Herod AA, Kandiyoti R. Energy
Fuels 2007;21:286.
HT-2D-GC as a new powerful technique to study conversion [24] Marsman JH, Wildschut J, Evers P, de Koning S, Heeres HJ. J Chromatogr A
processes of heavy cuts. 2008;1188:17.
[25] Frysinger GS, Gaines RB. J Sep Sci 2001;24:87.
[26] Gaines RB, Frysinger GS. J Sep Sci 2004;27:380.
Acknowledgments [27] Rathbun W. J Chromatogr Sci 2007;45:636.
[28] Dutriez T, Courtiade M, Thiébaut D, Dulot H, Bertoncini F, et al. J Chromatogr A
2009;1216:2905.
Teams of Jeremy Ponthus and Isabelle Merdrignac are warmly
[29] Beens J, Janssen HG, Adahchour M, Brinkman UAT. J Chromatogr A
acknowledged, respectively, for the analysis of VGO samples by 2005;1086:141.
MS Fischer method and for the LC fractionation of heavy samples. [30] Fisher IP, Fischer P. Talanta 1974;21:867.