Organic Geochemistry 95 (2016) 21–28

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Organic Geochemistry
journal homepage: www.elsevier.com/locate/orggeochem

Group-type characterization of crude oil and bitumen. Part I: Enhanced

separation and quantification of saturates, aromatics, resins and
asphaltenes (SARA)
K. K. (Adry) Bissada ⇑, Jingqiang Tan ⇑, Ewa Szymczyk, Mike Darnell, Mei Mei
Center for Petroleum Geochemistry, Department of Earth and Atmospheric Sciences, University of Houston, TX 77204-5007, United States

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

Article history: Compositional analysis of crude oils is very important along the entire value chain of the oil industry,
Received 14 October 2015 from upstream to midstream and downstream operations. An essential step of this analysis is to separate
Received in revised form 19 January 2016 crude oil into fractions of saturate hydrocarbon (saturates), aromatic hydrocarbon (aromatics), resins,
Accepted 10 February 2016
and asphaltenes (SARA). Though a number of methods have been developed for SARA separation, tradi-
Available online 16 February 2016
tional methods involve significant drawbacks that include, but are not limited to, inconsistent results
among labs and methods, extensive cross-contamination, and poor analytical precision. Here, we report
Keywords:
on a novel automated multi-dimensional high performance liquid chromatography (AMD-HPLC)
SARA separation
Oil group-type characterization
approach to enhance group-type characterization of crude oil or bitumen. The AMD-HPLC system is fully
High performance liquid chromatography automated and developed based on a combination of adsorption and partition chromatography. It is
Crude oil/bitumen composition equipped with a cyano column and a silica column. Each set of SARA columns is connected in series
via multi-position valves that allow a given column to be inserted ‘‘in” or to be bypassed ‘‘out” of the flow
path of the mobile phase at pre-set times in the process. In practice, a bitumen or oil sample of 0.02 g is
dissolved in a solvent mixture of 15% methanol, 15% acetone, and 70% chloroform, and injected into the
instrument. The sample is fractionated into the four groups by selective retention through interactions
with the solvent mobile phases and the column substrates. The instrument then resets and is ready to
start the next run. The entire analysis cycle requires about 60 min per run, including system re-
conditioning. Based on its wide application at our laboratory, the AMD-HPLC is characterized by high effi-
ciency, elimination of cross-contamination, and high reproducibility – when compared to traditional
methods.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction
The compositional analysis of crude oils provides important
information that impacts petroleum exploitation at every step
along the value chain, from exploration through production, trans-
portation, and refining. In upstream operations, geochemical inver-
sion of crude oil to the provenance of petroleum is invaluable in
petroleum system analysis, especially where source-bed informa-
tion may be difficult or impossible to obtain during exploration
(Bissada et al., 1992; Magoon and Dow, 1994). In reservoir man-
agement, crude oil composition is essential for fluid correlation
and the construction of functional, effective static reservoir models
⇑ Corresponding authors.
E-mail addresses: kbissada@central.uh.edu (K. K. (Adry) Bissada), jtan8@central.
uh.edu (J. Tan).
(Peters and Fowler, 2002; Anand and Freedman, 2012). In addition,
identifying the composition of asphaltenes, paraffins, and diamon-
doids in the crude and monitoring their susceptibility to precipi-
tate fouling agents within the reservoir and production stream
can avert formation damage and the clogging of flow line and pro-
duction equipment (Leontaritis et al., 1994; Escobedo and
Mansoori, 1995; Leontaritis, 2005; Soulgani et al., 2011). With
regard to midstream operations, dissolved and suspended colloids
and other organic solids, such as asphaltenes and diamondoids, can
precipitate out of solution and flocculate. In many instances, this
can result in the complete clogging of flow lines and in serious
damage to storage vessels and processing equipment (Vazquez
and Mansoori, 2000; Mansur et al., 2012). Furthermore, because
the emulsion stability of crude oil-water systems is highly depen-
dent on the amounts of interfacially active fractions, an awareness
of the relative abundance of resins and asphaltenes in high water-
cut oils is important to production and transportation planning

http://dx.doi.org/10.1016/j.orggeochem.2016.02.007
0146-6380/Ó 2016 Elsevier Ltd. All rights reserved.
22 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28
(Aske et al., 2002; Santos et al., 2014). In terms of downstream
operations, the mixing of crude oils from different sources, such
as possibly incompatible ‘‘opportunity crudes” in a refinery run,
may cause asphaltene self-aggregation and severe asphaltene
deposition in processing facilities (Rassamdana et al., 1996;
Adebiyi and Thoss, 2014). The solubility of asphaltenes, the heavi-
est fraction in any crude oil, depends on the delicate balance
between this fraction and the lighter fractions of the crude. Any
disturbance in this balance could lead to asphaltene self-
aggregation (Leontaritis and Mansoori, 1988). In refining and pro-
cessing operations, asphaltene self-aggregation and precipitation
can cause a wide variety of problems, from equipment and flow-
line plugging to catalyst deactivation (Speight, 1999; Gawel
et al., 2005).
An important step in this analysis is the group-type separation
of the components of petroleum fluid into saturate hydrocarbon
(saturates), aromatic hydrocarbon (aromatics), resins and
asphaltenes (SARA) (Jewell et al., 1972, 1974). Saturates compris-
ing nonpolar hydrocarbons, i.e., paraffins, iso-paraffins and naph-
thenes (PIN), are the most valuable fraction of crude oil.
Aromatics containing one or more aromatic or thiophenic rings
are polarizable hydrocarbons. However, resins and asphaltenes
are non-hydrocarbon fractions and abundant in polar substituents
containing nitrogen, sulfur and/or oxygen. These separations are
necessary to determine the relative concentration of each chemical
group and to obtain high-purity fractions for subsequent analyses
by gas chromatography, gas chromatography mass spectrometry
and isotope-ratio mass spectrometry (13C and 2H).
A number of procedures to identify and measure SARA fractions
have been developed, including the gravimetric adsorption chro-
matography (ASTM, 2012a,b,c), thin layer chromatography-flame
ionization detection (TLC-FID) (Karlsen and Larter, 1991; Jiang
et al., 2008), high performance liquid chromatography (HPLC)
(Suatoni and Swab, 1975; Hayes and Anderson, 1985; Grizzle and
Sablotny, 1986; Hayes and Anderson, 1986, 1988; Robbins, 1998;
Fan and Buckley, 2002), and automated asphaltene determinator
coupled with saturates, aromatics, and resins separation (SAR-
AD) (Schabron and Rovani, 2008; Boysen and Schabron, 2013;
Adams et al., 2015). Unfortunately, the gravimetric method is time
and resource consuming, requiring a couple of hours or longer for a
single run, as well as a large quantity of solvents, adsorbents, and
oil. Traditional HPLC cannot provide fully resolved separations of
saturates, aromatics and resins, while asphaltenes show either
irreversible adsorption or precipitation on the column (Boysen
and Schabron, 2013). Although the TLC-FID is a fast approach, the
FID response varies significantly among components even within
individual fractions (Masson et al., 2001; Bisht et al., 2013), and
the method cannot be recommended for routine SARA analysis of
medium and low gravity oils (Fan and Buckley, 2002). In addition,
analytical results from these approaches will differ from method to
method and commonly show poor reproducibility, which, in turn,
leads to confusion if the users are not familiar with the analytical
details (Kharrat et al., 2007).
To enhance SARA separation and quantification of crude oil and
bitumen, here we report on an automated multi-dimensional high
performance liquid chromatography (AMD-HPLC) technology
developed and widely used at the Center for Petroleum Geochem-
istry of the University of Houston. It uses a set of two columns and
is based on a combination of adsorption and partition chromatog-
raphy. A series of one to six crude oil or bitumen samples can be
analyzed successively without extensive sample preparation and
asphaltene separation. Once a sample is loaded, the computer-
controlled instrument runs fully automated and completely
unattended during fractionation and column regeneration. Com-
pared to conventional methods, this technology is characterized
by its high efficiency, lower cross-contamination, and high perfor-
mance. In addition, the system also allows for an immediate and
automatic further separation of saturates into individual PIN frac-
tions, which will be summarized elsewhere (Bissada et al., 2016).
2. Traditional SARA methods and drawbacks
SARA methods separate crude oil into fractions according to
their solubility in solvents of differing polarity and their affinity
for absorption on solid granular packing columns, e.g., natural clays,
silica gel and alumina. Gravimetric adsorption chromatography,
HPLC, and TLC-FID are the traditional methods to separate the SARA
fractions, and have been employed widely for several decades
(Jewell et al., 1972; Suatoni and Swab, 1975; Karlsen and Larter,
1991). Nevertheless, analyses of the same oil sample vary
significantly from lab to lab and with the method used (Karlsen
and Larter, 1991; Fan and Buckley, 2002; Kharrat et al., 2007),
leading to debates regarding aspects of their effectiveness,
accuracy, and quantitative capability (Fan and Buckley, 2002; Wu
et al., 2012; Bisht et al., 2013; Boysen and Schabron, 2013; Adams
et al., 2015).
Gravimetric adsorption chromatography was the earliest ver-
sion of approaches developed for SARA separation (Jewell et al.,
1972,1974). Because asphaltenes can irreversibly absorb to the sta-
tionary phase, the first step of this procedure is to precipitate the
asphaltene fraction with an excess of alkane solvent, commonly
either n-pentane, n-hexane, or n-heptane (Fig. 1). The more
recently developed SAR-AD method automates this separation by
precipitating asphaltenes onto a telfon packed column that are
then resolubilized and collected (Boysen and Schabron, 2013;
Adams et al., 2015). After deasphalting, maltenes (i.e., the fraction
that remains dissolved) then successively passed through two col-
umns, for example, a clay-packed column and a silica-gel column,
to adsorb resins and aromatics, respectively. The non-adsorbed
remaining oil components are quantified as saturate hydrocarbons.
Organic solvents such as toluene or benzene are then used to des-
orb and recover the resin and aromatic fractions. Variations in the
procedures can use a single silica gel or a mixture alumina-silica
gel column and different solvent systems. Although the American
Society for Testing and Materials (ASTM) has recommended vari-
ous versions (ASTM, 2012a,b,c), this method has been widely crit-
icized due to the time needed, the large quantity of oil and solvents
required, the poor precision, and the difficulty of automating the
process (Karlsen and Larter, 1991; Fan and Buckley, 2002; Boysen
and Schabron, 2013).
Because asphaltenes are irreversibly absorbed or difficult to
remove from HPLC stationary phases, deasphalting whole crudes,
bitumens, and rock extracts prior to separation is a common prac-
tice in conventional HPLC separation methods (e.g., Sarowha et al.,
1997; Podgorski et al., 2013). Subsequent separation of maltenes
into saturates, aromatics, and resins is conducted using high per-
formance liquid chromatography equipped with amino, cyano, sil-
ica, or alumina columns. This method is faster and more automated
than gravimetric adsorption chromatography. However, there are
obvious limitations that involve the use of extensive column re-
equilibration or reactivation times, and considerable sample
preparation (Grizzle and Sablotny, 1986). The fractions of maltenes
are separated and quantified through different processes, and
incompletely precipitated asphaltenes and polar compounds can
be irreversibly adsorbed on the column, leading to poor recovery
and a fouling problem (McLean and Kilpatrick, 1997; Fan and
Buckley, 2002; Boysen and Schabron, 2013). In addition, the com-
monly used refractive index (RI) detection method is very sensitive
to hydrocarbon components and solvents, thus generally requiring
frequent calibrations (Boysen and Schabron, 2013).
 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28 23

Fig. 1. Traditional SARA separation scheme.

The TLC approach has also been widely used for SARA separa-
tion (Karlsen and Larter, 1991; Jiang et al., 2008). This method
measures crude oil using silica rods as the stationary phase and
subsequently evaporating the elution solvents and successively
passing the rods through flame ionization detection (FID) to deter-
mine the relative amounts of SARA fractions. The deasphaltening
step is not necessary for this method. In addition, the TLC-FID sig-
nificantly accelerates the measuring speed and uses only a small
amount of crude oil. The SARA fractions from this approach are
often well-resolved. However, the quantitative results are obtained
based on an assumption that each fraction has an identical FID
response factor, which could actually vary significantly for polar
fractions. This method is better suited for low API crude oil or bitu-
men, rather than for medium or high API crude oils (Fan and
Buckley, 2002; Bisht et al., 2013; Boysen and Schabron, 2013).
Moreover, some of the polar compounds may remain on the TLC
rod, and some aromatics may act like resins during the separation
process. Thus, the separation and quantification of polar fractions
Fig. 2. Inconsistencies among labs using the traditional SARA separation method.
may be problematic, and the analytical results show a large
amount of error for repeat analysis (Masson et al., 2001; Jiang
et al., 2008). procedure was performed by four different laboratories, including
Extensive observations on the effectiveness of these traditional our own (UH).
methods have revealed serious inadequacies (Fan and Buckley, As Figs. 2–6 illustrate, significant drawbacks appear: (1) exper-
2002; Kharrat et al., 2007; Boysen and Schabron, 2013; Adams imental results are inconsistent among labs, (2) the separated
et al., 2015). Here, we re-examined a conventional open column SARA fractions are of variable purity, and (3) analytical precision
liquid chromatography method to determine its precision and reli- is poor. Fig. 2 shows the results of an oil sample respectively mea-
ability. After obtaining an initial weight of oil or bitumen, the sured in four labs using gravimetric adsorption chromatography
asphaltenes are precipitated with n-heptane. The weight of the with identical procedures. The results vary significantly. Compara-
asphaltene and maltenes portions are recorded. The maltenes por- tively, the asphaltenes fraction is higher than 10% in the results
tion is further separated using liquid chromatography column with from lab A, but lower than 2% in the results from lab D. The propor-
a series of solvents to separate the saturates, aromatics, and resins tions of resin measured in all labs are quite close, accounting for 8–
fractions. The column consists of a 40 cm long glass tube, 1 cm in 10%. The aromatics fraction exhibits strong variations of between
diameter, outfitted with a Teflon stop-cock at the bottom and 12% and 28% and shows the lowest and highest values in lab B
packed with 15 to 20 ml of 100–200 mesh silica gel retained by a and UH, respectively. In addition, the saturates from lab B is higher
wad of glass wool jammed into the bottom of the tube. The solvent than 60%, but that of other labs falls between 40% and 50%. Incom-
for saturates is n-heptane, for aromatics is toluene, and for resins is plete separation and possibly cross-contamination were revealed
a mixture of chloroform/methanol (
3:1). Each of these fractions is by gas-chromatography (GC), gas-chromatography/mass spec-
collected and quantified through rotary evaporation and gravimet- trometry (GC-MS), ultraviolet (UV) spectroscopy, and most vividly
ric method. The weight percent of each component is calculated by HPLC re-chromatography of typical SARA fractions derived from
from the total weight of asphaltenes and maltenes. The exact the traditional separation methods (Figs. 3 and 4). The saturates
24 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28
Fig. 3. Poor separation of group-types. GC, GC/MS, and HPLC re-chromatography of
SARA fractions pre-separated by third-party labs (using the conventional deas-
phaltening and open-column or medium-pressure liquid chromatographic separa-
tion of maltenes) revealed extensive cross contamination of the provided SARA
fractions.
Fig. 4. Fraction cross-contamination in conventional SARA analysis (SARA fractions
pre-separated by commercial laboratory using traditional asphaltene precipitation
and subsequent liquid chromatography of the maltenes. Each fraction of SARA was
then re-separated using the same procedure).
Fig. 5. GC analysis of the saturates from conventional SARA separation shows
incomplete separation and possible cross contamination of saturates by aromatics.
contains a large number of aromatics, while the aromatics includes
a large number of asphaltenes and a small number of resins. Fig. 4
illustrates that nearly 26% of the saturates comprises aromatics,
resins and asphaltenes, while nearly 49% of the aromatics fraction
is resins and asphaltenes. With regard to resins, 69% of this fraction
comprises aromatics and asphaltenes. It seems that the
Fig. 6. Poor precision. Precision of the conventional SARA group-type analysis was
determined by running twenty (20) replicate samples of C15+ bitumen from New
Albany Shale through the conventional asphaltene precipitation/open-column
liquid chromatography/gravimetry process. Note particularly the poor precision
of the Asphaltene precipitation step.
asphaltenes fraction has the highest purity, containing only 4% of
resins. In addition, most saturates can easily be separated, whereas
asphaltenes could exist extensively in all other fractions. The cross-
contamination of saturates by aromatics was also exhibited by GC-
FID and GC-photo-ionization detector results (GC-PID) (Fig. 5). In
Fig. 5 and 20 replicate bitumen samples from New Albany Shale
were measured with a conventional asphaltene precipitation/
open-column liquid chromatography/gravimetry process. It shows
a 7–8% deviation for the saturates, aromatics, and resins and a
nearly 50% deviation for the asphaltenes fraction.
3. AMD-HPLC SARA separation technology
3.1. Method and procedure
To enhance the efficiency, precision and reproducibility of SARA
separation and quantification, an AMD-HPLC crude oil analyzer was
developed (Fig. 7). It is a fully automated instrument capable of run-
ning either SARA or PIN separations, at the option of the analyst. A
series of one to six samples can be analyzed successively without
extensive sample preparation and prior asphaltene separation,
and the system will run completely unattended. The separation sys-
tem, as depicted in Fig. 7, is based on a combination of adsorption
and partition chromatography. It is equipped with a set of two col-
umns, a ‘‘SARA 1” column (S1, 900 x1/200 O.D.) packed with alkyl
nitrile (cyano column) and a ‘‘SARA 2” column (S2, 900 x1/200 O.D.)
packed with silica (silica column). The cyano column is selected
because of its unique selectivity for polar organic compounds
(e.g., asphaltenes and resins), while the silica column allows to
retain moderately polar organic compounds (e.g., aromatics). Col-
umns are connected in series via multi-position valves that allow
a given column to be inserted ‘‘in” or to be bypassed ‘‘out” of the
flow path of the mobile phase at pre-set times in the process.
In the process, a pre-weighed sample of 0.02 g of crude oil or
bitumen is dissolved in 300 ll of a mixture of 15% methanol:
15% acetone: 70% chloroform (MAC) and loaded into one of six
350 ll loops mounted on a 12-port, 6-position auto-sampling
valve. The SARA process proceeds in 4 steps as depicted in Fig. 7.
In step 1, both the S1 and S2 columns are inserted into the flow
path of the mobile phase. Hexane, the first mobile phase, sweeps
the sample solution out of the sample loop and injects it into the
S1 column. The S1 column will retain the resins and asphaltenes
near the inlet. The saturates and aromatics are carried forward
straight through the S1 column and on into the S2 column, which
retains the aromatics near the inlet, but allows the saturates to
pass through to the saturates port of the fraction collector.
 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28 25

Fig. 7. The AMD-HPLC SARA group-type separation process. The MAC solvent is a mixture of methanol, acetone and chloroform.

In step 2, the S2 column (with the retained aromatics) is
bypassed out of the flow stream. A second, slightly more polar
mobile phase consisting of a mixture of 94% hexane and 6% chloro-
form is pumped (instead of hexane alone), and the flow path is
reversed. This allows the new mobile phase to back-flush the resins
out of the front end of the S1 column and into the resins port of the
fraction collector.
In step 3, the mobile phase is changed to a much more polar sol-
vent mixture consisting of MAC (15% methanol:15% acetone: 70%
chloroform) which back-flushes the asphaltenes out of the front
end of the S1 column and into the asphaltene port of the fraction
collector.
In step 4, the S2 column (with the retained aromatics) is re-
inserted into the system and the S1 column is by-passed. A fourth
mobile phase (chloroform) is pumped, still in the reverse flow
mode, through the S2 column to back-flush the Aromatics out of
the front end of the S2 column and into the Aromatics port of
the fraction collector.
Once a sample is injected, the computer-controlled instrument
runs unattended during fractionation and column regeneration.
The instrument resets itself and is ready to start the next run.
The entire analysis cycle requires about 60 min per run, including
system re-conditioning. In the auto-sampling mode, the process is
repeated automatically until all samples are run. Quantification of
the products of AMD-HPLC can be done with gravimetry or evapo-
rative light scattering detection (ELSD).
non-solubility criteria showed radically improved purity of separa-
tions and significantly enhanced precision (Figs. 8–10) compared
to traditional methods (Figs. 3–6). Although incomplete separation
still occurs in all SARA fractions (Fig. 8), the proportions of retained
saturates in the aromatics fraction (Fig. 9) and that of retained aro-
matics in the resins and asphaltenes fractions (Fig. 10) are less than
1%. Furthermore, the analysis time is considerably shortened to
60 min compared to a couple of hours or longer for the ASTM gravi-
metric methods (ASTM, 2012a,b,c) and 4 h for methods like SAR-
AD (Boysen and Schabron, 2013; Adams et al., 2015).
A C15+ bitumen of the New Albany Shale was separated 20 times
using the AMD-HPLC and the open column methods, respectively
(Fig. 11). The AMD-HPLC method shows much higher precision
than the open-column methods. The standard deviations of SARA
fractions of AMD-HPLC are between 2% and 8%, whereas those of
conventional methods are between 12% and 46%.
3.4. Quantification of SARA fractions
One of the primary difficulties in SARA analysis is quantification
of the fractions, because the different fractions do not have com-

3.2. Samples

For the purpose of this paper, a standard oil sample with 29.6 °
API was separated by AMD-HPLC, and SARA fractions were then
examined by GC-FID, GC-PID and GC-MS to determine the extent
of possible cross contamination.
In addition, C15+ bitumen from the New Albany Shale, Illinois,
was measured repeatedly using the gravimetric conventional sep-
aration method and the AMD-HPLC, respectively, to compare the
standard deviations and quantification capabilities.

3.3. Results and discussion

Extensive testing of chromatographic performance using infra-

red and NMR spectroscopy, FID/PID GC, GC/MS, and solubility/ Fig. 8. Performance of the AMD-HPLC for SARA separation.
26 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28

Fig. 9. Aromatic fraction separated by the AMD-HPLC process. Left: total ion chromatogram; right: GC/MS trace (m/z 71 scan) on aromatic fraction shows < 1% saturates
retained in the aromatic fraction.

Fig. 10. GC/MS traces (m/z 71–253) of the resins and asphaltenes fractions show < 1% saturates or aromatics retained in the resins and asphaltenes fractions.

Fig. 12. The modified ELSD equipment (Alltech 500) for quantification of the SARA
fractions from the AMD-HPLC system.

mon chromophores or properties that allow quantification by typ-

Fig. 11. Enhanced precision of SARA separation by the AMD-HPLC process.
ical detectors for liquid chromatography. Currently this is usually
performed gravimetrically after evaporative removal of the sol-
vents prior to the weighing step. However, solvent evaporation
can result in significant loss of light components (C15) from the
recovered fractions. The procedure typically involves mild heating
under a N2 gas flow and it is difficult to control the consistency in
the amount of volatile removed with the solvent evaporation.
 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28
Fig. 13. AMD-HPLC separation with ELSD quantification vs. conventional separation with gravimetric quantification for C15+ bitumen samples of New Albany Shale. The
gravimetric method is illustrated in Fig. 1.
Some traditional SARA methods purposely top the crude oil prior
to SARA analysis by distilling under atmospheric or reduced pres-
sure so that the volatiles are uniformly removed. While this prac-
tice does allow for higher precision and mass balance, it sacrifices a
significant portion of the crude for further analysis. Other proce-
dures are designed to maximize volatile recovery. Wu et al.
(2012) developed the volatiles-SARA (VSARA) method to control
the lost volatile loss. This method uses open column liquid chro-
matography with nitrogen cooling at every step along the SARA
separation. Loss of volatiles can be controlled to < 5% using the
VSARA method.
We have developed an ELSD technique for quantification of the
fractions in their virgin solutions from the AMD-HPLC system
(Fig. 12). It entails injection of a 100 ll aliquot of the solutions from
the AMD-HPLC fractions into the ELSD solvent stream as it passes
through the injection port nebulizer of the ELSD detector. Detector
response is calibrated using synthetic solutions of the various
group-types in ranges of concentration as customarily encountered
in most crude oils. The method is much less susceptible to errors
stemming from loss of light components, and is, therefore, more
suitable for analyzing relatively high API crude oil and bitumen.
We have found that it is especially useful where diamondoids need
to be preserved in the saturate fraction for further analysis.
We have tested ELSD detection for typical oils (API gravity 28–
30°) and C15+ bitumen, and subsequently compared the results to
those from gravimetric analysis. The results conform well to with
from gravimetric methods (Fig. 13). As expected, however, results
for light oils and condensates (45–50° API) show marked differ-
ences. In addition, mass-balance computations of a crude oil sam-
ple from the North Sea indicated that the volatile-loss amount for
conventional quantitative method can be as high as 32%, whereas
that of ELSD is only 2% (Bissada et al., 2016).
Nevertheless, strictly speaking, volatile loss in the ELSD cannot
be fully avoided. Khan and Brett (2004) reported that the lost
amount of volatiles in the ELSD of vacuum gas oils (topped with
27
a temperature of 343 °C) can even reach 35%. Volatile loss for the
ELSD comes primarily from maltenes, and includes saturated and
aromatic constituents. The asphaltene determinator method
allows one to calculate and correct the total amount of volatile loss
from maltenes based on a comparison between the total ELSD peak
areas of the sample and the total ELSD peak areas of a quality con-
trol experiment (Boysen and Schabron, 2013). However, determin-
ing the amount of saturate and aromatic loss individually is not
possible. More recently, Adams et al. (2015) developed a vacuum
distillation method to prevent volatile loss in the ELSD. This
approach uses a quantitative vacuum distillation apparatus to dis-
till and capture volatile components, and a modified SAR-AD sys-
tem and a nuclear magnetic resonance spectroscope to measure
SARA fractions. Although the lost amount of volatile is < 1%
(Adams et al., 2015), the method is time consuming and not easily
implemented. Novel developments are still needed for a more pre-
cise quantification of SARA analysis.
4. Conclusions
The compositional analysis of crude oils is a very important step
along the entire industry value chain, one which significantly
impacts many operations in the upstream, midstream and down-
stream. An essential step of this analysis is SARA separation and
quantification. Although a number of procedures for SARA separa-
tion have been developed and used for decades, most show serious
inadequacies. In the current research, several crude oil samples
were measured to reveal the common drawbacks of the conven-
tional deasphaltening and open-column or medium-pressure liq-
uid chromatography method. This method was revealed to have
significant problems with (1) inconsistency among labs, (2) incom-
plete fractional separation, and (3) poor precision.
We reported an AMD-HPLC method to enhance the group-type
characterization for crude oil or bitumen. It is a fully automated
instrument developed using a combination of adsorption and
28 K. K. (Adry) Bissada et al. / Organic Geochemistry 95 (2016) 21–28
partition chromatography. The instrument is equipped with a
cyano column packed with alkyl nitrile and a silica column. Each
SARA set is connected in series via multi-position valves that allow
a given column to be inserted ‘‘in” or to be bypassed ‘‘out” of the
flow path of the mobile phase at pre-set times in the process. Based
on its wide application in our laboratory, the AMD-HPLC is charac-
terized by high efficiency, elimination of cross-contamination, and
high reproducibility compared to traditional methods. Although
the system generally shows good performance, further attention
should be paid to the separation of resins and asphaltenes as well
as the quantification of volatiles. Therefore, future efforts and novel
developments are still needed.
Acknowledgement
We deeply appreciate Clifford Walters, Joe Curiale, and an
anonymous reviewer for their comments and suggestions, and
thank the funding support from Ontex-Technology.
Associate Editor—Clifford C. Walters
References
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