Energy & Fuels 2002, 16, 1571-1575 1571

Rapid and Accurate SARA Analysis of Medium Gravity

Crude Oils
Tianguang Fan and Jill S. Buckley*
New Mexico Petroleum Recovery Research Center, New Mexico Institute of Mining and
Technology, Socorro, New Mexico

Received May 31, 2002

Crude oils can be described compositionally by a number of methods. SARA analysis is widely
used to divide crude oil components according to their polarizability and polarity using a family
of related analytical techniques. Problems arise because the analytical techniques do not
necessarily produce identical results. Users of the data, however, rarely distinguish between the
different techniques, assuming that SARA fraction values generated by any of the commonly
used methods are essentially interchangeable. We examine this assumption for medium gravity
crude oils and three SARA analysis methods: gravity-driven chromatographic separation, thin-
layer chromatography (TLC), and high-pressure liquid chromatography (HPLC). Results for a
suite of six crude oil samples show that a significant volume of volatile material that contains
both saturates and aromatics is lost in the TLC analysis. An improved HPLC method is introduced
that gives analyses comparable to the ASTM-recommended chromatographic method in less time
than that required for TLC analysis. An internal consistency test is recommended for evaluating
SARA fraction data.

Introduction methods, first introduced by Suatoni and Swab.3 Early

Analysis of the composition of crude oils can be
endlessly complex; the amount of detail collected should
be dictated by the application for which the data is
needed. One simple analysis scheme is to divide an oil
into its saturate, aromatic, resin, and asphaltene (SARA)
fractions. The saturate fraction consists of nonpolar
material including linear, branched, and cyclic satu-
rated hydrocarbons. Aromatics, which contain one or
more aromatic rings, are more polarizable. The remain-
ing two fractions, resins and asphaltenes, have polar
substituents. The distinction between the two is that
asphaltenes are insoluble in an excess of heptane (or
pentane), whereas resins are miscible with heptane (or
pentane). This classification system is useful because
it identifies the fractions of the oil that pertain to
asphaltene stability; it thus should be useful in identify-
ing oils with the potential for asphaltene problems.
SARA analysis began with the work of Jewell et al.1
Three main approaches have been used to separate
crude oils and other hydrocarbon materials into SARA
fractions. A clay-gel adsorption chromatography method
is the basis of ASTM D2007-93.2 This method requires
a fairly large oil sample, is time-consuming and difficult
to automate, and requires large quantities of solvents.
Improved methods fall into two groups. In the first
group are high-pressure liquid chromatographic (HPLC)
* Corresponding author. Fax: 1-505-835-6031. E-mail: jill@
prrc.nmt.edu.
(1) Jewell, D. M.; Weber, J. H.; Bunger, J. W.; Plancher, H.; Latham,
D. R. Anal. Chem. 1972, 44, 1391-1395.
(2) ASTM D2007-93: “Standard Test Method for Characteristic
Groups in Rubber Extender and Processing Oils by the Clay-Gel
Adsorption Chromatographic Method,” ASTM, 1993.
HPLC techniques used silica or alumina columns to
separate lighter petroleum fractions. The developments
in preparation of the bonded phase of HPLC columnss
especially NH2-bonded materialssmade it practical to
separate heavier fractions of petroleum samples.4-8
HPLC techniques are faster, more reproducible, and
more readily automated than the ASTM column tech-
nique. In both cases, however, it is necessary to remove
the asphaltene fraction before proceeding with the
chromatography. Asphaltenes are either irreversibly
adsorbed or precipitated during the saturate elution
step, and quantitative recovery cannot be achieved.9
The fastest separation method uses thin-layer chro-
matography (TLC) on quartz rods that are coated with
sintered silica particles. Unlike the column and HPLC
techniques, asphaltenes need not be separated from
other crude oil components before chromatographic
analysis. A popular technology known as the Iatroscan
that combines TLC with flame ionization detection
(TLC-FID) was first applied by Suzuki10 to automate
quantitative SARA separations, a method which has
(3) Suatoni, J. C.; Swab, R. E. J. Chromatogr. Sci. 1975, 13, 361-
366.
(4) Miller, R. Anal. Chem. 1982, 54, 1742-1746.
(5) Radke, M.; Willsch, H.; Welte, D. H. Anal. Chem. 1984, 56, 2538-
2546.
(6) Grizzle, P. L.; Sablotny, D. M. Anal. Chem. 1986, 58, 2389-2396.
(7) Félix, G.; Thoumazeau, E.; Colin, J. M.; Vion, G. J. Liq.
Chromatogr. 1987, 10, 2115-2132.
(8) Chaffin, J. M.; Lin, M. S.; Liu, M.; Davison, R. R.; Glover, C. J.;
Bullin, J. A. J. Liq. Chromatogr., Relat. Technol. 1996, 19, 1669-1682.
(9) McLean, J. D.; Kilpatrick, P. K. Energy Fuels 1997, 11, 570-
585.
(10) Suzuki, Y. 21st Annual Meeting of the Japan Society for
Analytical Chemistry, 1972; 47 (in Japanese).

10.1021/ef0201228 CCC: $22.00 © 2002 American Chemical Society

Published on Web 10/29/2002
1572 Energy & Fuels, Vol. 16, No. 6, 2002
Table 1. Crude Oil Sample Properties
density at 20 °C
oil °API (g/cm3)
A-95 25.2 0.8956
C-LH-99 22.6 0.9161
C-R-00 31.3 0.8673
S-Ven-39 28.8 0.8795
SQ-95 37.2 0.8409
Tensleep-99 31.1 0.8685
since been used extensively.11,12 Barman13 compared
SARA analyses of heavy hydrocarbon distillates by the
clay-gel and TLC-FID methods. TLC-FID uses very
small amounts of sample. SARA fractions in a crude oil
sample are often well-resolved using established devel-
opment procedures. Quantitative results are obtained
from peak areas, assuming that each SARA fraction has
an identical FID response factor.
Comparisons of SARA fraction measurements by
different techniques, usually from different laboratories,
can show large differences. To some extent, these
differences might be realscaused by the use of different
samples. In this work, identical samples were examined
by several different techniques to illuminate the
strengths and weaknesses of each. An improved HPLC
technique and a test for internal consistency in SARA
data are presented.
Experimental Materials and Methods
Crude Oils. Six medium-gravity, dead crude oils, varying
in API gravity from 22.6 to 37.2°, were used in this study.
Selected physical and chemical properties are shown in Table
1 (reproducible to at least (5 in the least significant digit
shown for each measurement). Densities were measured using
a Mettler/Paar DMA 40 with a circulating water bath for
temperature control. API gravities were calculated from
measured densities, corrected to 60 °F. Average molecular
weight (MW) was determined by freezing point depression
(Precision Systems Cryoscope 5009). Kinematic viscosities
were measured in Cannon-Fenske viscometers and converted
to absolute viscosity units. The amounts of asphaltene pre-
cipitated by n-heptane (1 g oil:40 mL heptane) ranged from
1.3 to 8.7%. Refractive index (RI) was measured with an Index
Instruments GPR11-37 automatic refractometer. PRI is the
RI of a mixture of oil and the least amount of heptane in which
asphaltene aggregates can be observed microscopically (at a
magnification of about 320×). The difference between RI of
the oil sample and PRI is a measure of asphaltene stability.14
ASTM Column Separation. Each of the crude oils was
tested using the full ASTM-recommended procedure (ASTM
D2007-932) using n-hexane to separate the asphaltenes. The
ASTM procedure is a chromatographic separation of the non-
asphaltic oil components through two columns: an Attapulgite
clay-packed column adsorbs the resins and a second column
packed with activated silica gel separates aromatics from the
saturate fraction. A 50:50 mixture of toluene and acetone is
used to recover the resin fraction from the clay packing. The
aromatics can be recovered by Soxhlet extraction of the silica
gel in hot toluene. Volatile components lost during the process
are calculated by weight difference.
TLC-FID. An MK-5 Iatroscan (Iatron Labs Inc., Tokyo),
equipped with a flame ionization detector (FID), interfaced
(11) Karlsen, D. A.; Larter, S. R. Org. Geochem. 1991, 17, 603-617.
(12) Vela, J.; Cebolla, V. L.; Membrado, L.; Andres, J. M. J.
Chromatogr. Sci. 1995, 33, 417-424.
(13) Barman, B. N. J. Chromatogr. Sci. 1996, 34, 219-225.
(14) Buckley, J. S.; Hirasaki, G. J.; Liu, Y.; Von Drasek, S.; Wang,
J. X.; Gill, B. S. Pet. Sci. Technol. 1998, 16, 251-285.
Fan and Buckley
MW n-C7 asph
(g/mol) RI at 20 °C PRI (%)
236 1.5128 1.4513 8.7
268 1.5137 1.4231 2.8
235 1.4851 1.4444 1.9
240 1.4976 1.4465 5.8
213 1.4769 1.4223 1.3
270 1.4906 ∼1.44 4.1
Figure 1. Separation of paraffins from single- and double-
ring aromatics.
with a model 203 PeakSimple data system (SRI Instrument),
was used to scan silica-coated quartz rods (Chromarod-SIII,
Iatron Laboratories). The rods were 15.2 cm long and 1.0 mm
in diameter, with a uniform coating of 5.0 µm silica particles
(pore diameter 60 Å). The FID detector was operated with a
pure grade of hydrogen at a flow rate of 160 mL/min; air at a
flow rate of 2.0 L/min was supplied by a pump; scan speed
was 60s/scan.
Crude oil samples were dissolved in HPLC grade dichloro-
methane (DCM) at a concentration of 20 mg/mL. A 1 µL
repeating syringe (Alltech Associate, Inc.) was used to spot
10 to 20 µg of sample on freshly activated rods. Development
steps included exposure to HPLC grade hexane for 30 min,
HPLC grade toluene for 10 min, and a 95:5 mixture of DCM
and methanol for 4 min. The rods were dried in air for 3 min
between solvent exposures. This treatment produced four well-
resolved peaks representing saturates, aromatics, resins, and
asphaltenes. Evaporative losses during the development steps
were evaluated by tests of similarly treated preparative thin-
layer chromatography plates for which changes in weight could
be measured and by comparison of peak sizes for undeveloped
rods.
HPLC. The HPLC chromatographic separation system
consisted of a Model 110A pump (Beckman), an R401 dif-
ferential refractometer (Waters), a U6K universal injector
(Waters), a Model 7040 high-pressure switching valve (Rheo-
dyne), and a Waters 486 UV detector (Millipore). Analogue
signals from the RI detector were interfaced to the model 203
PeakSimple data acquisition system (SRI Instrument). Two
3.9 × 300 mm µBondapak NH2 columns with 10 µm packing
(Waters) were used in series for chromatographic separation
of crude oil. The UV detector was operated at a wavelength of
254 nm to monitor elution of each fraction.
Selectivity of the columns was tested using mixtures of
known compounds. Mixtures of n-decane (C10), n-tridecane
(C13), n-pentadecane (C15), and n-octadecane (C18) in hexane
eluted as a single peak, as did hexane solutions of toluene and
1,3-diisopropylbenzene (DIPB). Hexane solutions of a single-
ring aromatic (DIPB) with a two-ring compound (1-methyl-
naphthalene or 1-MN) eluted as two well-resolved peaks.
Mixtures of the hexane solutions of DIPB, 1-MN, and C15
eluted as three distinct peaks (Figure 1).
Crude oil (1-mL) was weighed and dissolved in 40 mL of
hexane in an open-top screw cap vial with a Teflon/silicon
septum. After 48 h, a sample of maltenes dissolved in hexane
was withdrawn through a 0.2 µm PTFE syringe filter. The
withdrawn maltene solution was sealed in a 5-mL crimp-top
SARA Analysis of Medium Gravity Crude Oils
Figure 2. HPLC separation of C-R-00 maltenes.
Table 2. RI Detector Calibration
class hydrocarbon signal (area/mg)
saturates n-heptadecane 4647
1-ring aromatics DIPB 7088
2-ring aromatics 1-MN 12517
3-ring aromatics phenanthrene 16022
glass vial with an aluminum seal and PTFE/silicon septum.
The precipitated asphaltenes were recovered by filtration
through a 0.22 µm filter, dried, and weighed. Several 0.5 mL
aliquots of the maltene/hexane mixture were injected onto the
HPLC columns, using a gastight HPLC syringe (Hamilton).
Saturates and aromatics were eluted with hexane at a flow
rate of 1.5 mL/min. The amounts of saturates and aromatics
were calculated from peak areas using calibration factors
measured for known compounds (Table 2). Standard deviations
for peak areas of known compounds were less than 1% of the
measured values. A typical chromatogram is shown in Figure
2.
Resins were strongly adsorbed and did not elute with
hexane. A 30% (v/v) dichloromethane/hexane backflush was
used to elute the resins accumulated from at least three
replicate injections to ensure that sufficient resins could be
collected for accurate gravimetric determination of the amount
of resin remaining after solvent evaporation.
The principal improvements in the HPLC method described
here over previously proposed HPLC techniques include the
following: (i) analysis of the saturate and aromatic fractions
without solvent evaporation, thus avoiding the uncertainties
due to evaporation of some of the more volatile material along
with the solvent; and (ii) improved gravimetric quantification
of the amount of resins eluted by backflushing the columns
after repeated injections of maltenes.
Results and Discussion
The SARA fractions measured by all three techniques
are summarized in Figure 3. The results of the ASTM
method provide a baseline against which other SARA
separation methods can be compared. Table 3 shows the
results of t-tests applied to TLC-FID and HPLC results
paired with those obtained by the ASTM method for the
same oil to determine statistical significance of the
differences in the data.
TLC-FID vs ASTM. Comparisons between ASTM
and TLC-FID results show consistent, statistically
significant differences for all fractions except the as-
phaltenes (Table 3). The amount of volatile material lost
before the detector response is recorded is not routinely
recognized or measured. That amount is as high as 60%
in this study, all of which comes from the saturate and
aromatic fractions. If fractions were apportioned on the
basis of peak areas summed to 100%, ignoring the
volatile material, the amounts of resins and asphaltenes
Energy & Fuels, Vol. 16, No. 6, 2002 1573
Table 3. Pairwise t-tests for Significance of Differences
between SARA Methodsa
p-valuesb
fraction ASTM vs TLC-FID ASTM vs HPLC
saturates <0.0001 0.0236
saturates + volatiles 0.0049 0.8192
aromatics 0.0064 0.1634
resins 0.0443 0.0914
asphaltenes 0.2214
a Statistically significant differences are highlighted in bold
italic type. b p is the probabilty that the samples come from
different populations; p < 0.05 indicates that differences between
the results of different measurement methods are statistically
significant.
would be consistently overestimated. Since the amount
of volatile material has been measured in this study, it
might be included in the saturate and aromatic frac-
tions, but additional information is needed on how to
apportion it between these two fractions. Summation
of the volatile and saturate amounts from the TLC-
FID method would significantly overestimate the satu-
rate fraction and underestimate the amount of aromat-
ics. Only by separating all of the volatile material up to
some fairly high boiling point (Karlsen and Larter11
measured losses of approximately 50% of n-C14, which
boils at 253.5 °C; whereas the loss of n-C16 , which boils
at 286.8 °C, was negligible) and analyzing that fraction
separately, then combining the two sets of data would
one be able to apply the TLC-FID technique to medium
gravity oil samples with any confidence, but the advan-
tage of rapid analysissthe main reason for using this
techniqueswould be lost. Apportioning the high molec-
ular weight polar materials between resins and asphalt-
enes, which is always based, rather arbitrarily, on
solvency, inevitably will vary from the ASTM and HPLC
methods as well since the solvents used are not identi-
cal. On the basis of these comparisons, the TLC-FID
technique cannot be recommended for routine SARA
analysis of medium gravity oils.
HPLC vs ASTM. Differences between the improved
HPLC SARA fractions and those measured by the
ASTM-recommended method were mainly in the volatile
and saturate fractions. There were no losses to evapora-
tion in the HPLC technique, unlike the ASTM method
in which there were some losses (during evaporation of
the solvent after removal of the asphaltenes and in the
various fraction recovery and solvent evaporation pro-
cesses). However, if all of the volatile material lost in
the ASTM measurements was assumed to belong to the
saturate fraction, the amounts of saturates, aromatics,
and resins determined by the ASTM and HPLC methods
were statistically indistinguishable (see Table 3). The
measurement technique for the amount of asphaltenes
is the same for both methods, hence asphaltenes were
determined only once. The major differences between
the two techniques are the amounts of time, sample,
and solvent required. For both techniques, there is a
two-day period required for separation of the asphalt-
enes. Beyond that, however, the HPLC technique re-
quires only about 1 h per sample including three
replicate separations of saturates and aromatics and
backflushing of the column to elute resins, compared
to at least 20 h for the ASTM separation. One gram of
oil is adequate to give the same accuracy by the HPLC
technique as the 10 g required by the ASTM test. The
1574 Energy & Fuels, Vol. 16, No. 6, 2002
Figure 3. Comparison of SARA fractions determined by the ASTM method, by the improved HPLC method, and by TLC-FID.
solvent requirements are on the order of 300 mL and 2
L per sample for the HPLC and ASTM tests, respec-
tively.
Internal Consistency of SARA Fraction Data.
There are many variations of the specific analyses, all
of which are referred to by the acronym of SARA, but
not all of which give equivalent results. Since the details
of the separation technique are not always provided, a
method is needed to evaluate SARA data from unspeci-
fied tests so that ASTM and HPLC data can be distin-
guished from TLC-FID results. A simple evaluation
scheme is shown here, based on comparisons between
the SARA fraction data and API gravity, which is almost
universally reported for stock-tank oil samples.
A group of 87 crude oils was evaluated using the
HPLC technique described above. The SARA fraction
Fan and Buckley
data thus obtained were used to find regression coef-
ficients that correlate the percentages of each fraction
with the API gravities measured for the same samples.
The following empirical relationship was obtained:
˚APIcalculated ) 74.5 - 0.306 × S - 0.385 ×
A - 1.08 × R - 0.763 × As (r2 ) 0.68)
where S is the wt % of saturates, A is the wt % of
aromatics, R is the wt % of resins, and As is the wt %
of asphaltenes. A plot of measured vs calculated API
gravity is shown in Figure 4.
To test the consistency of any set of SARA fraction
data, similar plots can be prepared, as illustrated for
the ASTM and the TLC-FID data sets. Despite some
scatter, the ASTM data clearly follow the predicted
SARA Analysis of Medium Gravity Crude Oils
Figure 4. An estimate of API gravity obtained from SARA
fraction data can be compared to the measured API gravity
as a test of the internal consistency of the SARA data. A
correlation was developed with 87 different crude oil samples
spanning the range from about 15 to over 40°API, tested with
the HPLC technique. The ASTM data set closely reproduces
the correlation, whereas there is no correlation between the
SARA fraction data from TLC-FID measurements and API
gravity of the oil.
trend (r2 ) 0.76), whereas there is no correlation
between the TLC-FID data and API gravity measured
for the same samples. Note that it is not sufficient to
test a single oil sample. It is the trend for oils with
varying properties over a range of API gravity that is
diagnostic. The correlation should be applied only over
Energy & Fuels, Vol. 16, No. 6, 2002 1575
the gravity range of the samples that were used in its
development, i.e., from a low value of about 15 to a high
of about 40°API.
Conclusions
•Measurements of SARA fractions are highly depend-
ent on methodology. Results of different methods may
not be comparable. Caution is needed in comparing
results, even from similar methods.
•The TLC-FID technique cannot be used to test
medium gravity oils without considerable additional
analysis to account for components that boil at temper-
atures up to 250 °C. The apportioning of high molecular
weight, polar, aromatic material into asphaltenes and
resins does not correspond to the asphaltenes and resin
fractions defined by the ASTM method.
•An efficient HPLC methodology has been developed
and shown to correspond closely to the more time-
consuming ASTM-recommended method of SARA analy-
sis.
•SARA fraction data can be tested for internal con-
sistency by comparing API gravity values calculated
from the SARA fractions with measured values of API
gravity for the same oil sample.
Acknowledgment. The authors thank Dr. Jianxin
Wang for many useful discussions. This work was
supported by the National Energy Technology Labora-
tory (NETL) of the US DOE through contract DE-AC26-
99BC15204 and by support from industrial sponsors
including BP, Chevron, Gaz de France, IFP, Norsk
Hydro, and TotalFinaElf. Crude oils were provided by
ARCO, Chevron, Shell, and the University of Wyoming.
EF0201228