Fuel xxx (2012) xxx–xxx

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

Predicting SARA composition of crude oil by means of NMR

Felipe Sanchez-Minero a,⇑, Jorge Ancheyta b, Guadalupe Silva-Oliver a, Sergio Flores-Valle c
a
Departamento de Ingeniería Química Petrolera, ESIQIE, Instituto Politécnico Nacional, Zacatenco, Mexico City 07738, Mexico
b
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Mexico City 07730, Mexico
c
Laboratorio de Catálisis y Materiales, ESIQIE, Instituto Politécnico Nacional, Zacatenco, Mexico City 07738, Mexico

h i g h l i g h t s

" We characterize five crude oils by means of NMR and SARA analysis.
" We obtain aromaticity factors from NMR data.
" We propose an equations system to predict the SARA concentration from aromaticity factors.

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

Article history: Five crude oils with a wide range of API gravities were characterized by means of nuclear magnetic res-
Received 23 April 2012 onance (1H NMR and 13C NMR) and SARA (saturates, aromatics, resins, and asphaltenes) composition.
Received in revised form 3 October 2012 From NMR analyses, the concentrations of aromatic-hydrogen (Har) and aromatic-carbon (Car) were
Accepted 11 October 2012
obtained, with which the corresponding aromaticity factors FHA and FCA were calculated. Aromaticity fac-
Available online 25 October 2012
tors were used to develop correlations to predict the SARA concentration of crude oils. The developed cor-
relations showed good accuracy when comparing experimental and calculated values.
Keywords:
Ó 2012 Elsevier Ltd. All rights reserved.
NMR
SARA
Aromaticity
Correlations

1. Introduction
Characterization of petroleum is typically carried out by stan-
dardized ASTM methods, such as true boiling point distillation,
API gravity, and elemental analysis (C, H, N, and S). The results of
all these analytic techniques are reported as crude oil assay, which
can go just from a few analyses up to very detailed characterization
of the oil and of its distillated fractions [1,2]. SARA (saturates, aro-
matics, resins, and asphaltenes) analysis is frequently done as part
of assay of petroleum, which among other applications is used for
predicting the compatibility/stability of blends of crude oils to
anticipate problems of sedimentation during storage and transpor-
tation [3]. SARA composition has been also recently reported to be
used for kinetic modeling studies in the molecular reconstruction
when dealing with heavy oil hydrocracking [4,5].
Other specialized techniques, such as nuclear magnetic reso-
nance (NMR), are not common for characterizing crude oils; how-
ever some studies have revealed that NMR can indeed be used for
such a purpose no matter the API gravity of the petroleum sample
[6,7]. This is a great advantage since due to the heaviness of some
low API gravity oils; various conventional methods are not suitable
for analyzing this type of samples [8–13].
The experimental results of structural characterization as deter-
mined by NMR have been used to develop correlations to calculate
different properties of petroleum and its fractions. C/H atomic ratio
and contents of paraffins, naphthenes and aromatics are some of
the properties that are reported to be calculated from 1H and 13C
NMR data [14–16]. As for SARA composition, Molina et al. [17] re-
ported correlations to predict it from 1H NMR, but their study was
limited to vacuum residua.
Developing correlations for predicting SARA composition of
crude oils with a wide range of API gravity (10–33°) is the main
objective of this work. To do that, NMR results were used to obtain
the concentration of aromatic-hydrogen and aromatic-carbon,
from which aromaticity factors were computed and correlated to
SARA analysis.
2. Experimental

⇑ Corresponding author. Five crude oils with different API gravity were used. The
E-mail address: jfsanchezm@ipn.mx (F. Sanchez-Minero). crudes were labeled as A (32.8° API), B (27.1° API), C (21.2° API), D

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.10.027

Please cite this article in press as: Sanchez-Minero F et al. Predicting SARA composition of crude oil by means of NMR. Fuel (2012), http://dx.doi.org/
10.1016/j.fuel.2012.10.027
2 F. Sanchez-Minero et al. / Fuel xxx (2012) xxx–xxx

(13.1° API) and E (10.3° API). The crude oils were characterized by
using the following methods:
 Elemental composition (hydrogen and carbon) was obtained
with a Leco TCH-600 model analyzer according to ASTM
D5291 method. Sulfur concentration was determined following
the ASTM D4294, using a Tanaka RX-306SH model analyzer.
 SARA concentration was determined in two steps. Firstly,
asphaltenes were precipitated with n-heptane by means of
ASTM D3279 method. The remaining maltenes fraction was
separated in accordance with ASTM 2700 method, obtaining
in this way the concentration of resins, aromatics and saturates.
 The 1H and 13C NMR spectra of crude oils were determined in a
Varian Oxford NMR spectrometer operating at 1H and 13C reso-
nance frequency of 300 and 75 MHz, respectively, accumulating
64 scans for hydrogen and 1000 scans for carbon spectra. NMR
spectra were obtained in deuterated chloroform (CDCl3) solu-
tions, in accordance with ASTM D5292 method. Tetramethylsil-
ane was used as internal reference in these solvents for
assigning the 0.0 parts per million (ppm) chemical shift position
in both 1H and 13C NMR. Integrals of the aromatic hydrogen
band were corrected by subtracting the signal of residual chlo-
roform, from 7.25 ppm chemical shift, in the predominantly
chloroform-d solvent.
For 1H spectra, samples were prepared by dissolving about
30 mg of oil in 0.8 mL of chloroform-d, to set a concentration close
to 5% v/v. Solid particles were removed by filtration to obtain a
homogeneous solution by common procedures. For 13C spectra,
samples were prepared by dissolving 1 mL of oil and 1.0 mL of deu-
terated chloroform. Samples were filtered through a cotton-packed
Pasteur pipette. A flip angle of 30° was set up and tube diameter of
5 mm were used for samples. Spectra were recorded from 2 to
14 ppm for hydrogen and from 10 to 250 ppm for carbon. Rotor
spin was set up at 20 Hz. Delay time was set up at 15 s for 1H
and 90 s for 13C.
3.2. SARA analysis
The results of SARA analysis are also reported in Table 1. The
concentration of saturates and aromatics (mono-, di- and tri-rings)
decreases as the API gravity of the crude oil diminishes, whereas
the concentration of resins and asphaltenes exhibits the opposite
tendency. Thus, the higher concentration of saturates and aromat-
ics in the lightest crude oil is related to a great content of naphtha,
whereas the higher concentration of resins and asphaltenes in the
heaviest crude oil is related to a great content of residue.
3.3. Nuclear magnetic resonance analysis
NMR spectra of crude oils were analyzed to obtain the concen-
tration of aromatic- and aliphatic-hydrogen, as well as aromatic
and aliphatic-carbon. For 1H NMR spectrum, the total aromatic-
hydrogen was obtained from the integral in the region from 6 to
9 ppm, whereas for the total aliphatic-hydrogen it was obtained
in the region of 0.5–5 ppm. For 13C NMR spectrum, the total aro-
matic-carbon and the total aliphatic-carbon were obtained in the
region of 110–160 ppm and 10–60 ppm, respectively. Both spectra
are shown in Fig. 1, where the different regions are illustrated.
From NMR analysis (1H NMR and 13C NMR), the aromaticity factors
of hydrogen (FHA) and carbon (FCA) for each crude oil were obtained
with the following equations [20,21]:

3. Results and discussion

3.1. Elemental analysis

The five crude oils used in this study show a wide range of API
gravity values (10.3–32.8°), with very different composition as can
be observed in Table 1. The H/C molar ratio calculated from the ele-
mental analysis indicates that crude A (the lightest one, 32.8° API)
exhibits higher concentration of saturated hydrocarbons (high va-
lue of H/C ratio), while crude E (the heaviest one, 10.3° API) is con-
centrated in unsaturated hydrocarbons, such as asphaltenes. In the
case of sulfur, the already-known typical tendency was found, that
is the heavier the crude oils the higher its sulfur content. This
behavior has also been reported by others [18,19].

Table 1
Elemental and SARA analyses of various crude oils.

Crude oil A B C D E
API gravity 32.8 27.1 21.2 13.1 10.3
Elemental analysis
H/C molar ratio 1.67 1.62 1.55 1.47 1.43
Sulfur (wt.%) 1.06 2.58 3.64 5.14 5.92
SARA analysis
Saturates (wt.%) 51.62 43.15 32.10 25.38 20.01
Aromatics (wt.%) 31.35 29.95 26.34 17.04 11.36
Resins (wt.%) 14.25 18.20 25.82 31.41 36.26
Asphaltenes (wt.%) 2.78 8.70 15.74 26.17 32.37
Fig. 1. 1H and 13
C NMR spectra of crude oils.

Please cite this article in press as: Sanchez-Minero F et al. Predicting SARA composition of crude oil by means of NMR. Fuel (2012), http://dx.doi.org/
10.1016/j.fuel.2012.10.027
 F. Sanchez-Minero et al. / Fuel xxx (2012) xxx–xxx 3

Table 2
Aromaticity factors of crude oils.

Crude oil A B C D E
API gravity 32.8 27.1 21.2 13.1 10.3
Aromaticity factor
FHA 0.0249 0.0352 0.0491 0.0632 0.0772
FCA 0.1194 0.1375 0.2058 0.2695 0.2860

Har
F HA ¼ ð1Þ
Har þ Hal

C ar
F CA ¼ ð2Þ
C ar þ C al
where Har is the total aromatic hydrogen, Hal the total aliphatic
hydrogen, Car the total aromatic carbon, and Cal the total aliphatic
carbon.
The values of FHA and FCA calculated with Eqs. (1) and (2) are
presented in Table 2. Both factors decrease with the increased
API gravity of the crude oil. This trend is similar to that observed
for the concentration of resins and asphaltenes of the crude oil,
which indicates that these fractions strongly affect the aromaticity
factors.

3.4. Development of correlations

SARA concentration of the crude oils was correlated with the

aromaticity factors. Fig. 2 presents the concentration of aromatics,
resins and asphaltenes (ARA) for each crude oil as a function of FHA
and FCA factors. The fraction of saturates was not plotted since it
does not contain aromatic structures. Aromaticity factors have a
direct dependency with resins and asphaltenes contents while
with aromatics content it is inverse. This means that the types of
molecules that contribute to increase the aromaticity of a crude
oil are not those with a few aromatic rings but those with highly
concentrated aromatic structures such as asphaltenes.
Then, the results of Fig. 2 were used to develop the correlations
to predict SARA composition as function of aromaticity factors. The
tendency curve observed for each ARA component was selected to
propose the correlations, based on their higher values of R2 (>0.98).
The best set of parameters of the proposed correlations was ob-
tained by using the Powell minimization method with the Scientist
of MicroMath software. The following correlations were derived:
ARA concentration as function of FHA:
% Aromatics ¼ 4090:3 F 2HA þ 31:0 F HA þ 32:9
% Resins ¼ 414:6 F HA þ 4:9
% Asphaltenes ¼ 561:6 F HA  10:5
ARA concentration as function of FCA:
% Aromatics ¼ 748:5 F 2CA þ 198:3 F CA þ 16:8
% Resins ¼ 113:9 F CA þ 2:38
% Asphaltenes ¼ 301:2 F 2CA þ 32:0 F CA  2:8
The concentration of saturates can be determined by difference:
% Saturates ¼ 100  % Aromatics  % Resins  % Asphaltenes
Fig. 3 presents the comparison between calculated and experi-
mental data of SARA concentration for each crude oil. The results
clearly illustrate that the developed correlations do not tend to
either over estimate or under estimate the SARA composition. In
Fig. 2. ARA concentration as a function of FHA (aromatics (h), resins (s) and
asphaltenes (e)) and FCA (aromatics (j), resins (d) and asphaltenes ()).
general, half of the points are on the right-hand side of the 45° line
and the other half on the left-hand side.
On the other hand, Table 3 shows the R2 values for each corre-
lation. The correlation to predict the concentration of resins pre-
ð3Þ sents the highest value of R2, whereas the correlation to predict
the concentration of asphaltenes exhibits the lowest value. In addi-
ð4Þ tion, the correlations as function of the aromaticity factors show
that FHA factor reaches higher precision than FCA factor. To verify
ð5Þ this, the mean absolute percentage error (MAPE) was calculated
using the following equation:
n  
ð6Þ 100 X 
Y exp  Y cal 
MAPE ¼  ð10Þ
n i¼1 Y exp 
ð7Þ
where n is the total number of experimental data, Yexp is the exper-
ð8Þ imental value and Ycal is the calculated value.
The correlations that use FHA factor present a MAPE value of
5.2%, whereas the correlations that use FCA factor reaches a MAPE
value of 11.5%. This is mainly due to the better prediction of
asphaltenes concentration from FHA compared with FCA. Finally,
ð9Þ
the ranges obtained from a residual analysis were 1.48/+1.78
and 3.56/+3.42 for FHA and FCA, respectively. This also confirms
the better prediction with FHA.
It is worth to mention that the developed correlations were
generated using five crude oils of a particular region with API

Please cite this article in press as: Sanchez-Minero F et al. Predicting SARA composition of crude oil by means of NMR. Fuel (2012), http://dx.doi.org/
10.1016/j.fuel.2012.10.027
4 F. Sanchez-Minero et al. / Fuel xxx (2012) xxx–xxx

gravity in the range of 10–33°, so that the results cannot be gener-

alized for other samples. To do that, it is mandatory to incorporate
a wider range of experimental data of characterization of crude oils
and of their respective asphaltenes fraction. In any case, the
proposed approach can serve as basis for development of a more
general correlation.

4. Conclusions

From the characterization of crude oils with different API grav-

ity and the use of experimental data to develop correlations, the
following conclusions can be pointed out:

(i) Aromaticity factors of the crude oil as determined from 1H

and 13C NMR vary directly with the concentration of asphalt-
enes and resins, and inversely with the content of aromatics.
(ii) Proper correlations to calculate SARA composition of crude
oil can be developed as function of aromaticity factors.

Acknowledgments

F.S-M. and G.S-O. acknowledge the financial support from pro-

ject IPN-SIP-20111044. S.O. Flores thanks to NMR laboratory for
the provided facilities.

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Please cite this article in press as: Sanchez-Minero F et al. Predicting SARA composition of crude oil by means of NMR. Fuel (2012), http://dx.doi.org/
10.1016/j.fuel.2012.10.027