Journal of Petroleum Science and Engineering 168 (2018) 256–262

Contents lists available at ScienceDirect

Journal of Petroleum Science and Engineering

journal homepage: www.elsevier.com/locate/petrol

Application of high resolution NMR (1H and 13C) and FTIR spectroscopy for T
characterization of light and heavy crude oils
I.Z. Rakhmatullina, S.V. Efimova, V.A. Tyurina, A.A. Al-Muntaserb, A.E. Klimovitskiib,
M.A. Varfolomeevb, V.V. Klochkova,∗
a
Institute of Physics, Kazan Federal University, 18 Kremlevskaya St., Kazan, 420008, Russian Federation
b
Department of Physical Chemistry, Butlerov Institute of Chemistry, Kazan Federal University, 18 Kremlevskaya St., Kazan, 420008, Russian Federation

A R T I C LE I N FO A B S T R A C T

Keywords: High-resolution nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy ex-
Crude oil periments were applied to obtain detailed information on the hydrocarbon chemistry of three light and three
1
H NMR spectroscopy heavy crude oils. Quantitative fractions of aromatic molecules and functional groups constituting oil hydro-
13
C NMR spectroscopy carbons were determined by 13C NMR spectroscopy and comparative analysis of the oil samples with different
FTIR spectroscopy
viscosity, origin and preliminary treatment. SARA composition and some important information about ar-
SARA fraction
Functional group
omaticity, oxidation behavior, branching, aliphaticity and sulfurization of studied oil samples were obtained.
Integral characteristics of high-resolution NMR and FTIR spectra have a great potential to study the structure and
characterization of light and heavy crude oils, which could substitute present traditional fractionation proce-
dures. Relationships between spectroscopic parameters obtained by high-resolution NMR and FTIR spectroscopy
methods and crude oil compositions can be useful for fast prediction of crude oil properties due to different type
of treatment, including thermal methods for enhanced oil recovery. Also quantitative proportions of functional
groups obtained by NMR and spectral indices obtained by FTIR can be one of the criteria for developing fin-
gerprint approach.

1. Introduction
1
H and 13C NMR spectroscopy is well-known recognized technique
for establishing structural formulas, spatial and electronic structure of
either first synthesized or isolated from natural raw materials in-
dividual organic compounds (Usachev et al., 2013a, 2013b, 2017a;
Kononova et al., 2017; Rakhmatullin et al., 2015, 2017a;
Abdrakhmanov et al., 2017; Khodov et al., 2017). In recent years, there
has been a growing interest in using NMR spectroscopy for studying
various objects in petroleum chemistry (Gao et al., 2017; Mondal et al.,
2017; Alcazar-Vara et al., 2016; Smirnov and Vanyukova, 2014). The
NMR method opens wide opportunities in studying the structure of oil
disperse systems and determining their physical and chemical char-
acteristics. The NMR method can help to determine aromatic and ali-
phatic hydrogen and carbon atoms in crude oil samples. Areas under
resonance peaks in NMR spectra characterize the amount of 1H or 13C
atoms of corresponding chemical types. Integration of the peaks and
subsequent manipulations and calculations yield quantitative proton
and carbon type analyses (Kushnarev et al., 1989). 1H and 13C NMR can
be applied to obtain information on content of general functional
groups (tertiary and primary carbon atoms, aromatic cores) and pos-
sible presence of olefins or water impurity (Rakhmatullin et al., 2017b).
However, it has not been widely used yet for analysis of high-molecular
weight oil samples because of their complex structural organization.
Number of works on the NMR analysis of crude oils and petroleum
products, including oil residues, is limited. This circumstance is largely
due to the natural shift of interests towards the study of the properties
of heavy oil, for which the possibilities of NMR are limited. In parti-
cular, the correlation between viscosity of oil and relaxation times in
these objects is no longer observed clearly as for light oils, and the use
of pulsed NMR method is becoming increasingly problematic.
High resolution NMR spectroscopy has provided detailed chemical
information on the proton and carbon chemistry of petroleum materials
for over 60 years (Edwards, 2011). Today high resolution NMR in-
strumentation used to derive detailed multinuclear hydrocarbon in-
formation is based on superconducting magnet technologies (Derome,
1987; Rule and Hitchens, 2006; Kolosova et al., 2016; Usachev et al.,
2017b; Galiullina et al., 2017). In the case of oil and petroleum pro-
ducts containing typically hundreds of compounds, mainly hydro-
carbons, an important feature of NMR spectroscopy is a strict

∗
Corresponding author.
E-mail address: vladimir.klochkov@kpfu.ru (V.V. Klochkov).

https://doi.org/10.1016/j.petrol.2018.05.011
Received 19 January 2018; Received in revised form 28 April 2018; Accepted 1 May 2018
Available online 25 May 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
I.Z. Rakhmatullin et al.
correlation of integral intensities of separate groups of signals in certain
chemical shifts ranges in 1H and 13C NMR spectra with the content of
the corresponding molecular fragments (Holzgrabe, 2017; Poveda
et al., 2014; Da Silva Oliveira et al., 2014). Note that approaches widely
used in petrochemical methods of analysis, such as elemental (X-ray
fluorescence, absorption and emission optical spectroscopy), fragment
and component (IR spectroscopy, mass spectrometry, chromatography)
analyses are indirect (unlike NMR) because they require using reference
materials for quantitative investigations. It should also be noted that
the quantitative 13C NMR spectrum is the only direct method for
measuring aromaticity (Car) – relative percentage of aromatic carbon
atoms in hydrocarbons (McBeath et al., 2011; Fergoug and Bouhadda,
2014; Lee and Glavincevski, 1999).
SARA (saturates, aromatics, resins, and asphaltenes) analysis is
another important application in crude oil composition studies, because
these data are used for predicting the oil recovery using specific tech-
nology, the compatibility and stability of blends of crude oils to an-
ticipate problems of sedimentation during storage and transportation
(Aske et al., 2002). Some studies have revealed that NMR can be used
for predicting SARA composition of crude oils (Molina et al., 2010;
Sanchez-Minero et al., 2013). 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.
This allowed developing correlations for predicting SARA composition
of crude oils with a wide range of API gravity (10–33°) (Sanchez-Minero
et al., 2013).
FTIR spectroscopy has been an important analytical tool for de-
termining the chemical composition and structures of the components
of crude oils and their refined products for more than four decades
(Brown et al., 1975). Many of the early investigations emphasized the
isolation of various types of hydrocarbons, e.g., paraffins, naphthenes,
and olefins, from petroleum. Infrared spectra of all types of hydro-
carbons have been measured and catalogued by the National Bureau of
Standards, API Project 44 (American Petroleum Institute Project 44).
Since petroleum and the products of petroleum are mixtures of many
hydrocarbons, much emphasis has been placed on using IR spectra to
quantitatively measure the composition of mixtures. In addition to
measuring the composition of hydrocarbon mixtures this method has
been also used in determining the degree of branching in paraffins, e.g.,
methods have been suggested to determine the number of CH3 and CH2
groups in hydrocarbons (Rericha and Horak, 1967, 1968).
The aim of this study was to determine the qualitative and quanti-
tative composition of six different crude oil samples by means of the
high-resolution 13C NMR spectroscopy, FTIR spectroscopy and SARA
analysis and to find some general relationship between spectroscopic
parameters and crude oil composition. These relationships can be useful
for fast prediction of crude oil properties changing upon different type
of treatment, including thermal methods for enhanced oil recovery.
2. Materials and methods
Viscosity of the samples used in this study is reported along with the
extraction method in Table 1. There are three low viscosity oils (1), (2)
and (3), one semi-heavy oil (4), and two high viscosity oils (5) and (6).
These samples were provided by Tatneft, Zarubezhneft and RITEK oil
Table 1
Viscosity and extraction method of studied oil samples.
Sample number Viscosity, mPa*s Extraction method
1 7.5 high pressure air injection (HPAI)
2 5.95 primary recovery
3 37.2 high pressure air injection (HPAI)
4 106 primary recovery
5 2420 SAGD
6 49700 cyclic steam simulation (CSS)
257
Journal of Petroleum Science and Engineering 168 (2018) 256–262
companies. Crude oils (1), (3), (5) and (6) were extracted by thermal
enhanced oil recovery (EOR) methods.
2.1. NMR spectroscopy
NMR experiments on the studied oil samples (1–6) were performed
on a Bruker Avance II 500 NMR spectrometer. Field lock and shimming
were achieved using the deuterium signal from D2O in a glass capillary
placed into the 5 mm NMR tube together with the investigated oil
sample. All samples were studied without dilution. 1H NMR spectra
were recorded using 30° pulses (zg30 pulse program); acquisition time
was 4.7 s; pre-scan delay was 6.5 μs, and the relaxation delay between
scans was 2 s; spectrum width was 12.0 ppm (6000 Hz); 400 scans were
accumulated. 13C NMR spectra were recorded using 90° pulses with
inverse gated broadband proton decoupling (zgig pulse program); re-
laxation delay between pulses was 9 s (and acquisition time was 3.5 s);
spectrum width was set to 220.0 ppm; number of scans was 3200.
Exponential digital filter with the lb parameter of 10 Hz was applied to
process 13C NMR spectra prior to Fourier transformation.
Measurements were made at the temperature of 30 °C. All NMR spectra
were integrated after baseline correction, and a mean of at least three
integration values were taken for each calculation. The relative stan-
dard deviation of the results of manual integration did not exceed 3%.
Estimation of molar fractions of primary, secondary, tertiary, aromatic
and quaternary carbons was carried out in a way similar to our previous
work (Rakhmatullin et al., 2017b).
Information obtained by quantitative integration of aromatic signals
in individual spectral ranges is represented by the fraction of the cor-
responding carbon atoms relative to their total number. Fraction of
aromatic carbons Car can be straightforwardly found from NMR spectra:
Iar
Car = ,
∑j I j (1)
where Car is the fraction of aromatic carbons, Iar is the total integral
intensity of aromatic carbons and Ij is the integral intensity of all
functional groups in 13C NMR spectrum of the sample.
It is impossible to obtain unambiguous information on the content
of hydrocarbons (alkanes, cyclanes) from 13C NMR spectra, although
this information is contained in the fragmentary composition, which
can be determined with high accuracy (Kushnarev et al., 1989). If in-
tegral intensities of individual groups signals in the 13C NMR spectrum
are known, then corresponding molar fractions of tertiary, primary,
secondary and quaternary carbons can be calculated by the following
formulas (Kalabin et al., 2000):
Ct = ((1.04It − 0.034Isq)/(It + Isq + Ip))(1 − Car ), (2)
Cp = ((1.02Ip − 0.006Isq)/(It + Isq + Ip))(1 − Car ), (3)
Csq = ((1.04Isq − 0.04It − 0.02Ip)/(It + Isq + Ip))(1 − Car ), (4)
where Ct is the fraction of tertiary carbons; Cp – fraction of primary
carbons; Csq – fraction of secondary and quaternary carbons (due to the
complexity of separation of methylene and methine signals, their
summary contents is estimated); It is the total integral intensity of
tertiary (CH) groups; Isq – total integral intensity of secondary (CH2)
and quaternary groups, Ip – total integral Intensity of primary (CH3)
groups in 13C NMR spectrum of the oil sample.
Mean chain length (MCL) was calculated as:
Csq + Ct ⎞
MCL = 2∗ ⎜⎛ ⎟ + 2.
⎝ Cp ⎠ (5)
The aromaticity factor (FCA) can be calculated from the equation
(Sanchez-Minero et al., 2013):
Car
FCA = ,
Car + Cal (6)
I.Z. Rakhmatullin et al.
where Cal = Cp + Csq + Ct is the total aliphatic carbon content.
2.2. FTIR spectroscopy
Infrared spectra (4000–600 cm−1) were obtained using a Vertex 70
FTIR spectrometer (Bruker, Germany) equipped with a single reflection
ZnSe crystal ATR accessory (MIRacle, PIKE Technologies, USA), purged
under dry air to remove atmospheric water vapor. Background spectra
of 128 scans at a resolution of 4 cm−1 were subtracted from the sample
spectra. The data was processed in the OPUS 7.2 (Bruker) program.
Spectral coefficients (C1-5) were obtained as the ratios of the optical
density values (D) at the maxima of the corresponding absorption bands
according to the following equations (Permanyer et al., 2002; Borrego
et al., 1996; Kayukova et al., 2012; Abdrafikova et al., 2013; Al-
Muntaser et al., 2017):
D1600
C1 = ,
D720 (7)
D1710
C2 = ,
D1465 (8)
D1380
C3 = ,
D1465 (9)
D720 + D1380
C4 = , revealed for the treated samples 3 and 5.
D1600 (10)
D1030
C5 = , 13
D1465 (11)
where D1600 is the optical density of arenes; D1710 is the optical density
of oxidation products; D1380 of alkanes (methyl CH3– groups); D720 – of
long methylene chains (CH2 > 4); D1030 of sulfoxide groups; D1465 of
alkanes (methylene CH2– groups); C1 is the aromaticity index, C2, –
oxidation index, C3, – branching index, C4, – aliphaticity index, and C5
is the sulfurization spectral coefficient (Abdulkadir et al., 2016).
2.3. SARA fractionation
According to ASTM 2007 standard, oil samples were divided into
their fractions: saturates, aromatics, resins, and asphaltenes (SARA).
Asphaltenes were precipitated under the effect of a 40-fold amount of n-
alkane solvent, heptane. Heptane is chosen to preserve the light frac-
tions of oil. Maltenes were separated by means of liquid-adsorption
chromatography or open column on aluminum oxide calcined at 420 °C
into saturated hydrocarbons via their elution with heptane as an ad-
sorbent. Similarly, aromatic compounds were separated via their elu-
tion with toluene and resins, which were extruded from the adsorbent
with the aid of a solvents mixture, namely, toluene and isopropyl al-
cohol taken in equal proportions. The SARA separation scheme and
gravimetric method is illustrated in Fig. 1 (Bissada et al., 2016).
3. Results and discussion
3.1. NMR spectroscopy analysis
The 1H NMR spectra of studied oil samples 1–6 are shown in Fig. 2.
There are characteristic spectral regions of aliphatic and aromatic
proton signals in the high and low fields. Evidently, as the viscosity
increases, resonance signals broaden. The samples 1 and 2 are similar in
origin and viscosity, but the first was subjected to heat treatment. In the
middle area of the spectra protons of water (4.89 ppm) give a peak next
to the proton signal of water in the capillary (4.68 ppm). The only
difference between these spectra (1, 2) is due to the fact that the signal
from water protons has a four times greater integral intensity in sample
1 than in thermally untreated sample 2: (H2O:H2Oref = 8:1) in sample 1
vs. (H2O:H2Oref = 2:1) in sample 2. This fact agrees with the suggestion
258
Journal of Petroleum Science and Engineering 168 (2018) 256–262
Fig. 1. SARA separation scheme.
that during the oxidation process in the crude oil 1, some amount of
water appeared. The samples 3, 5 and 6 were also recovered by thermal
methods. The presence of the water protons signal in samples 5 and 6
was also observed due to formation of strong water emulsions in steam
injection processes. In the 1H NMR spectra of these samples, in addition
to broadening of resonance lines due to increased viscosity, weak sig-
nals from unsaturated hydrocarbon groups in the olefinic area were also
For a more detailed study of these samples, 13C NMR spectroscopy
was applied. The 13C NMR spectra of crude oils 1–6 are shown in Fig. 3.
C NMR spectroscopy is much more informative thanks to the wide
range of chemical shifts (200 ppm) of non-equivalent 13C nuclei
(Breitmaier and Woelter, 1986; Friebolin, 1991). Moreover, broadband
decoupling between 1H and 13C nuclei facilitates interpretation of 13C
NMR spectra. This method can be applied for analysis of mixtures
containing molecules of known type (Makhiyanov and Safin, 2006).
Crude oil contains vast number of compounds; however, spectral width
of 13C spectra still allows classifying them into several classes even if
individual components cannot be identified (Kalabin et al., 2000). 13C
NMR spectra contain numerous distinguishable signals, which can be
assigned to different typical regions and thus give information on the
fractions of primary (methyl groups CH3) – Cp, secondary (methylene
groups CH2) – Cs, tertiary (methine groups CH) – Ct, quaternary (C) – Cq
and aromatic Car types of carbon atoms. Estimating of the molar content
of various carbon groups (Cp, Csq, Ct, Car) made by integrating of the
corresponding regions in 13C NMR spectra was carried out in a way
similar to our previous work (Rakhmatullin et al., 2017b). Table 2
shows the obtained results.
A quantitative analysis of the composition of the oil samples studied
by NMR showed that for more viscous oils (5, 6), on the one hand, a
small decrease in the concentration of carbon groups in the aliphatic
region (Cp, Csq) is observed, and on the other hand, the concentration of
aromatic groups (Car) increases 3–4 times compared to light oils (1, 2).
For oils not exposed to the heat treatment (2, 4), a decrease in the
concentration of tertiary groups (Ct) and increase in the concentration
of secondary groups (Csq) is observed. Also, with increasing viscosity,
there is an obvious tendency to increase of the aromaticity factor (FCA)
and mean chain length (MCL). Aromaticity factor can be used for de-
veloping correlations for predicting SARA composition of studied oils
by NMR spectroscopy (Sanchez-Minero et al., 2013).
3.2. SARA analysis of studied oil samples
One of the common ways for studying the group composition of oil
is SARA analysis; analysis scheme is to divide an oil sample into its
saturate, aromatic, resin, and asphaltene (SARA) fractions (Fig. 1). The
saturate fraction consists of nonpolar material including linear, bran-
ched, and cyclic saturated hydrocarbons. Aromatics, which contain one
I.Z. Rakhmatullin et al. Journal of Petroleum Science and Engineering 168 (2018) 256–262

Fig. 2. 1H (500 MHz) NMR spectra of oil samples 1–6.

or more aromatic rings, are more polarizable. The remaining two
fractions, resins and asphaltenes, have polar substituents. The distinc-
tion between the two is that asphaltenes are insoluble in an excess of
heptane whereas resins are miscible with heptane (Tianguang et al.,
2002; Ashoori et al., 2017). The results of SARA analysis are reported in
Table 3.
3.3. FTIR spectroscopy analysis
3.3.1. FTIR spectra of oil samples
The FTIR spectra of studied oil samples 1–6 are shown in Fig. 4.
FTIR spectroscopy generates unique spectral signatures related to the
absorption pattern of the material. The infrared spectra are dominated
by the stretching aliphatic bands (v (CH3+CH2)) at 2923 and
2852 cm−1 and the deformation bands of methyl (1365 cm−1) and both
methyl and methylene groups (δ- (CH3+CH2), 1465 cm−1). They also
display distinct bands assigned to carbonyl and/or carboxyl groups (v-
(C = 0), 1705 cm−1) which is observed in the case of 6 sample and to
the stretching vibration of aromatic carbons (v (C=C), 1605 cm−1). In
the region 700-900 cm−1, various bands occur assigned to the out-of-
plane deformation vibration of one isolated aromatic C—H bond (γ
(CHar), 870 cm−1), two or three adjacent aromatic C—H bonds (γ
(CHar), 814 cm−1), and four adjacent aromatic C—H bonds (γ (CHar),
750 cm−1). In addition, the band assigned to the skeletal vibration of

13
Fig. 3. C (125 MHz) NMR spectra of crude oil samples 1–6.

259
I.Z. Rakhmatullin et al. Journal of Petroleum Science and Engineering 168 (2018) 256–262

Table 2 studied oils by IR spectroscopy, spectrometric indices (C1-C5) were

Molar fractions (%) of primary (Cp), secondary and quaternary (Csq), tertiary calculated according to equations (7)–(11) (Permanyer et al., 2002;
(Ct), aromatic (Car) groups, aromaticity factor (FCA) and mean chain length Borrego et al., 1996; Kayukova et al., 2012; Al-Muntaser et al., 2017).
(MCL) of aliphatic hydrocarbons based on13C NMR spectra of oil samples 1–6. The optical density values (D) were obtained as a maxima peak heights
Group type Sample number of selected and corresponding absorption bands. Spectrometric indices
were calculated from peak heights of selected infrared bands allow for a
1 2 3 4 5 6 better comparison of the spectra. This procedure is more reliable as it
Cp 32.0 33.6 24.5 18.8 17.5 14.7 takes into consideration several vibrations of the same type occurring
Csq 49.5 54.7 53.0 56.1 48.9 40.4 simultaneously (Permanyer et al., 2002). Tables 4 and 5 presents the
Ct 12.1 4.8 10.0 8.4 12.8 15.8 results of IR spectral analysis of the studied oil samples.
Car 6.4 6.9 12.5 16.7 20.8 29.1 As follows from the data in Table 5, an increasing in the index of
FCA 0.064 0.069 0.125 0.167 0.208 0.291
aromaticity (C1) and aliphaticity (C4) was observed depending on their
MCL 5.8 5.5 7.1 8.9 9.0 9.6
viscosity, but it is also noticeable that sample 4 falls out from this
tendency. For the index of oxidation C2 some changes was observed for
Table 3 oil samples depending on their extraction methods and viscosity.
SARA analysis (%) of studied oil samples. Sample 4, as well as sample 2, was not subjected to heat treatment. At
the same time, these samples differ remarkably in viscosity. So, such a
Sample number 1 2 3 4 5 6
sharp difference in the spectral indices for a more viscous and untreated
Saturates 65.51 67.70 49.79 59.62 26.20 30.96 sample 4 can be explained by its original characteristics. However,
Aromatics 24.60 23.52 31.89 26.71 40.60 39.18 some ambiguous changes are observed for the remaining spectral in-
Resins 9.21 8.29 14.87 12.08 28.49 14.17
dices: branching (C3) and sulfurization (C5), which can be related to the
Asphaltenes 0.68 0.49 3.46 1.59 4.70 15.69
difference in the origin of the investigated samples.
In order to reconcile the data obtained by both methods (NMR and
FTIR), the correlation between the Car value from NMR and C1 coeffi-
cient based of optical data was built. (Fig. 5).
Both values refer to the relative amount of aromatic cores, nor-
malized by the total intensity of carbon signals in NMR or to long
methylene chains in FTIR. While the aromaticity degrees obtained by
two methods vary in a concerted way for samples 1, 3, 5 and 6, the two
samples 2 and 4 stand out against this correlation. It is significant that
the latter two samples are primary recovery oils, while products 1, 3, 5,
6 were extracted by thermal EOR methods.

4. Conclusions

Based on the results of 1H, 13C NMR and FTIR spectroscopy ex-
periments, the important data about the “structure – property” char-
acterization of light and heavy oil samples were obtained, indicating a
great potential of these methods. From the 1H NMR characterization of
oils with different origin, viscosity and treatment performed, the fol-
lowing conclusions can be made: crude and refined oils are distin-
guishable both by estimating the ratio of proton concentrations of water
molecules and by observing signals in the olefinic area of spectra. From
the 13C NMR characterization of oils with different origin, viscosity and
treatment, the following conclusions can be pointed out: a decrease in
the concentration of tertiary carbon groups is observed in oil samples
which were not subjected to heat treatment; in the transition from light
to heavy oils, a decrease in the concentration of primary and an in-
crease in the concentration of aromatic carbons are observed.
Fig. 4. FTIR spectra of oil samples 1–6. An increase in the degree of aromaticity and aliphaticity is observed
from the FTIR spectroscopy analysis as we go from light to heavy oil
samples; also some changes in the degree of branching, oxidation,
more than four methylene groups (r (CH2)n, 720 cm−1) was observed.
sulfurization were identified. Thus, these results indicated that com-
Further, the most important peaks of the spectra are labelled including
bined use of high-resolution NMR and FTIR spectroscopy has a great
the aliphatic hydrocarbons, the aromatics and polyaromatics as well as
potential to study the structure and characterization of light and heavy
the carbonyls and aromatics (Mouillet et al., 2008; Feng et al., 2016;
crude oils, which could substitute present traditional fractionation
Van den bergh, 2011).
procedures. Relationships between spectroscopic parameters obtained
By moving from oil with low viscosity to high viscosity, there is an
by the above methods and crude oil compositions can be useful for fast
increasing in the intensities of the absorption bands characteristic of
prediction of crude oil properties changing upon different type of
aromatic and polyaromatics structures (1600 and 900-730 cm−1)
treatment, including thermal methods for enhanced oil recovery. Also,
which, along with changes in their spectral indices (Tables 4 and 5),
quantitative proportions of functional groups obtained by NMR and
indicates an increase in the degree of their aromaticity.
spectral indices obtained by FTIR can be one of the criteria for devel-
oping fingerprint approach.
3.3.2. Spectrometric indices calculation
To study the structural-group composition and characterization of

260
I.Z. Rakhmatullin et al. Journal of Petroleum Science and Engineering 168 (2018) 256–262

Table 4
Optical density values (D) at the maxima of absorption bands of oil samples 1–6 according to FTIR spectroscopy data.
Sample number Optical densities at the maxima of absorption bands

1710 cm−1 1600 cm−1 1465 cm−1 1380 cm−1 1030 cm−1 720 cm−1

1 0.217 0.143 0.859 0.514 0.280 0.337

2 0.215 0.094 0.820 0.494 0.267 0.277
3 0.023 0.257 0.771 0.435 0.135 0.464
4 0.025 0.156 1.826 0.972 0.203 0.540
5 0.035 0.190 0.816 0.497 0.175 0.338
6 0.203 0.239 1.507 0.902 0.117 0.393

Table 5 10.1080/01932691.2015.1116082.
Spectral coefficients (C) of oil samples 1–6 according to FTIR spectroscopy data. Al-Muntaser, A.A., Suwaid, M.A., Rakhmatullin, I.Z., Varfolomeev, M.A., 2017. Chemical
transformation of asphaltenes during thermal upgrading of heavy and extra-heavy
Sample number Spectrometric indices oils. In: SGEM2017 Vienna GREEN Conference Proceedings, vol. 17. pp. 75–82.
http://dx.doi.org/10.5593/sgem2017H/15/S06.010.
C1 C2 C3 C4 C5 American Petroleum Institute Project 44, National Bureau of Standards, (Washington,
D.C).
1 0.424 0.253 0.598 3.800 0.326 Ashoori, S., Sharifi, M., Masoumi, M., Salehi, M.M., 2017. The relationship between SARA
2 0.339 0.262 0.602 3.728 0.326 fractions and crude oil stability. Egypt. J. Pet. 26, 209–213. http://dx.doi.org/10.
3 0.554 0.030 0.564 7.574 0.175 1016/j.ejpe.2016.04.002.
Aske, N., Kallevic, H., Sjöblom, J., 2002. Water-in-crude oil emulsion stability studied by
4 0.288 0.014 0.532 9.717 0.111
critical electric field measurements. Correlation to physico-chemical parameters and
5 0.560 0.043 0.609 5.832 0.354
near-infrared spectroscopy. J. Pet. Sci. Eng. 36, 1–17. http://dx.doi.org/10.1016/
6 0.608 0.135 0.599 5.418 0.078 S0920-4105(02)00247-4.
Bissada, K.K.A., Tan, J., Szymczyk, E., Darnell, M., Mei, M., Zhou, J., 2016. Group-type
characterization of crude oil and bitumen. Part I: enhanced separation and quanti-
fication of saturates, aromatics, resins and asphaltenes (SARA). Org. Geochem 95,
21–28. http://dx.doi.org/10.1016/j.orggeochem.2016.02.007.
Borrego, A.G., Blanco, C.G., Prado, J.G., Díaz, C., Guillén, M.D., 1996. 1H NMR and FTIR
spectroscopic studies of bitumen and shale oil from selected Spanish oil shales.
Energy fuels. 10, 77–84. http://dx.doi.org/10.1021/ef950111x.
Breitmaier, E., Woelter, W., 1986. 13С NMR Spectroscopy. Methods and Application in
Organic Chemistry. Wiley-VCH ISBN 9783527264667.
Brown, C.W., Lynch, P.F., Ahmadjian, M., 1975. Applications of infrared spectroscopy in
petroleum analysis and oil spill identification. Appl. Spectrosc. Rev. 9 (1), 223–248.
http://dx.doi.org/10.1080/05704927508081491.
Da Silva Oliveira, E.C., Neto, A.C., Junior, V.L., De Castro, E.V.R., De Menezes, S.M.C.,
2014. Study of Brazilian asphaltene aggregation by nuclear magnetic resonance
spectroscopy. Fuel 117, 146–151. http://dx.doi.org/10.1016/j.fuel.2013.09.022.
Derome, A.E., 1987. Modern NMR Techniques for Chemistry Research, Oxford. Pergamon
press ISBN 9781483286426.
Edwards, J.C., 2011. A review of applications of NMR spectroscopy in the petroleum
industry. In: Nadkarni, R.A. (Ed.), Spectroscopic Analysis of Petroleum Products and
Lubricants. ASTM International, West Conshohocken, pp. 423–473.
Feng, Z.G., Bian, H.J., Li, X.J., Yu, J.Y., 2016. FTIR analysis of UV aging on bitumen and
its fractions. Mat. Struct. 49, 1381–1389. http://dx.doi.org/10.1617/s11527-015-
0583-9.
Fergoug, T., Bouhadda, Y., 2014. Determination of Hassi Messaoud asphaltene aromatic
structure from 1H & 13C NMR analysis. Fuel 115, 521–526. http://dx.doi.org/10.
1016/j.fuel.2013.07.055.
Fig. 5. Correlation between Car (from NMR data) and C1 (from FTIR data) for Friebolin, H., 1991. Basic One- and Two Dimensional NMR Spectroscopy, Weinhei. Wiley-
oil samples 1–6. VCH, Basel, N.-Y ISBN 0-89573-972-0.
Galiullina, L.F., Aganova, O.V., Latfullin, I.A., Musabirova, G.S., Aganov, A.V., Klochkov,
V.V., 2017. Interaction of different statins with model membranes by NMR data. BBA-
Acknowledgments Biomemb 1859, 295–300. http://dx.doi.org/10.1016/j.bbamem.2016.12.006.
Gao, Y., Zou, Y.-R., Liang, T., Peng, P., 2017. Jump in the structure of Type I kerogen
revealed from pyrolysis and 13C DP MAS NMR. Org. Geochem 112, 105–118. http://
The work has been performed according to the Russian Government dx.doi.org/10.1016/j.orggeochem.2017.07.004.
Program of Competitive Growth of Kazan Federal University. Also this Holzgrabe, U., 2017. Quantitative NMR, methods and applications. In: Lindon, J.C.,
work was partially supported by the subsidy allocated to Kazan Federal Tranter, G.E., Koppenaal, D.W. (Eds.), Encyclopedia of Spectroscopy and
Spectrometry (Third Edition). Academic Press, New York, pp. 816–823.
University for the state assignment in the sphere of scientific activities Kalabin, G.A., Kanitskaya, L.V., Kushnarev, D.F., 2000. In: Quantitative NMR
(VK – 3.5283.2017/6.7). Spectroscopy of Natural Organic Raw Materials and its Processing Products.
Chemistry, Moscow ISBN 5-7245-1169-X. [in Russian].
Kayukova, G.P., Kiyamova, A.M., Romanov, G.V., 2012. Hydrothermal transformations of
References
asphaltenes. Pet. Chem. 52, 5–14. http://dx.doi.org/10.1134/S0965544111060089.
Khodov, I.A., Maltceva, O.V., Klochkov, V.V., Koifman, O.I., Mamardashvili, N.Zh, 2017.
Abdrafikova, I.M., Ramazanova, A.I., Kayukova, G.P., Vandyukova, I.I., Petrov, S.M., N-confused porphyrins: complexation and 1H NMR studies. New J. Chem. 41,
Romanov, G.V., 2013. Structural-group Composition of Conversion Products of 7932–7937. http://dx.doi.org/10.1039/c7nj01814b.
Heavy Ashalchin Oil by Method of Ir-fourier Spectroscopy, vol. 7. Bulletin of the Kolosova, O.A., Usachev, K.S., Aganov, A.V., Klochkov, V.V., 2016. Antimicrobial peptide
Kazan Technological University, Kazan: Chemistry, pp. 237–242 ([in Russian]). protegrins interact with DPC micelles by apolar hydrophobic cluster: structural stu-
Abdrakhmanov, R., Blokhin, D., Usachev, K., Karataeva, F., Klochkov, V., 2017. NMR dies by high-resolution NMR spectroscopy. BioNanoSci 6, 317–319. http://dx.doi.
studies of the Mn2+ interactions with amyloid peptide Aβ13-23 in water environ- org/10.1007/s12668-016-0218-9.
ment. BioNanoSci 7, 204–206. http://dx.doi.org/10.1007/s12668-016-0317-7. Kononova, O., Litvinov, R.I., Blokhin, D.S., Klochkov, V.V., Weisel, J.W., Bennett, J.S.,
Abdulkadir, I., Uba, S., Salihu, A., Almustapha, M.N., 2016. A rapid method of crude oil Barsegov, V., 2017. Mechanistic basis for the binding of RGD- and AGDV-peptides to
analysis using FT-IR spectroscopy. Nig. J. Basic Appl. Sci. 24, 47–55. http://dx.doi. the platelet integrin αIIbβ3. Biochemistry 56, 1932–1942. http://dx.doi.org/10.
org/10.4314/njbas.v24i1.8. 1021/acs.biochem.6b01113.
Alcazar-Vara, L.A., Zamudio-Rivera, L.S., Buenrostro-González, E., 2016. Effect of as- Kushnarev, D.F., Afonina, T.V., Kalabin, G.A., Presnova, R.N., Bogdanova, N.I., 1989.
phaltenes and resins on asphaltene aggregation inhibition, rheological behaviour and Investigation of the composition of crude oils and condensates from the south of the
waterflood oil-recovery. J. Disper. Sci. Technol. 37, 1544–1554. http://dx.doi.org/ Siberian platform using 1H and 13C NMR spectroscopy. Pet. Chem. U.S.R.R 29,

261
I.Z. Rakhmatullin et al.
149–159.
Lee, S.W., Glavincevski, B.B., 1999. NMR method for determination of aromatics in
middle distillate oils. Fuel Process. Technol. 60, 81–86. http://dx.doi.org/10.1016/
S0378-3820(99)00013-2.
Makhiyanov, N., Safin, D., 2006. An NMR study of the structure and molecular char-
acteristics of polyether block copolymers based on propylene oxide and ethylene
oxide. Polym. Sci. Ser. B 48, 37–45. http://dx.doi.org/10.1134/
S1560090406010088.
McBeath, A.V., Smernik, R.J., Schneider, M.P.W., Schmidt, M.W.I., Plant, E.L., 2011.
Determination of the aromaticity and the degree of aromatic condensation of a
thermosequence of wood charcoal using NMR. Org. Geochem 42, 1194–1202. http://
dx.doi.org/10.1016/j.orggeochem.2011.08.008.
Molina, D.V., Uribe, U.N., Murgich, J., 2010. Correlations between SARA fractions and
physicochemical properties with 1H NMR spectra of vacuum residues from
Colombian crude oils. Fuel 89, 185–192. http://dx.doi.org/10.1016/j.fuel.2009.07.
021.
Mondal, S., Yadav, A., Kumar, R., Bansal, V., Das, S.K., Christopher, J., Kapur, G.S., 2017.
Molecular-level structural insight into clarified oil by nuclear magnetic resonance
(NMR) spectroscopy: estimation of hydrocarbon types and average structural para-
meters. Energy Fuels 31, 7682–7692. http://dx.doi.org/10.1021/acs.energyfuels.
7b00994.
Mouillet, V., Farcas, F., Besson, S., 2008. Ageing by UV radiation of an elastomer modified
bitumen. Fuel 87, 2408–2419. http://dx.doi.org/10.1016/j.fuel.2008.02.008.
Permanyer, A., Douifi, L., Lahcini, A., Lamontagne, J., Kister, J., 2002. FTIR and SUVF
spectroscopy applied to reservoir compartmentalization: a comparative study with
gas chromatography fingerprints results. Fuel 81, 861–866. http://dx.doi.org/10.
1016/S0016-2361(01)00211-3.
Poveda, J.-C., Molina, D.-R., Pantoja-Agreda, E.-F., 2014. 1H- and 13C-NMR structural
characterization of asphaltenes from Vacuum residua modified by thermal cracking.
CT&F 5, 49–60.
Rakhmatullin, I.Z., Galiullina, L.F., Garipov, M.R., Strel'nik, A.D., Shtyrlin, Y.G.,
Klochkov, V.V., 2015. Dynamic NMR study of dinitrophenyl derivatives of seven-
membered cyclic ketals of pyridoxine. Magn. Reson. Chem. 53, 805–812. http://dx.
doi.org/10.1002/mrc.4251.
Rakhmatullin, I.Z., Galiullina, L.F., Balandina, A.A., Garipov, M.R., Strelnik, A.D.,
Galiullina, A.S., Shtyrlin, Y.G., Klochkov, V.V., 2017a. Stereodynamics of some pyr-
idoxine derivatives. Magn. Reson. Chem. 55, 304–311. http://dx.doi.org/10.1002/
mrc.4528.
Rakhmatullin, I.Z., Efimov, S.V., Margulis, B.Ya, Klochkov, V.V., 2017b. Qualitative and
262
Journal of Petroleum Science and Engineering 168 (2018) 256–262
quantitative analysis of oil samples extracted from some Bashkortostan and Tatarstan
oilfields based on NMR spectroscopy data. J. Pet. Sci. Eng. 156, 12–18. http://dx.doi.
org/10.1016/j.petrol.2017.04.041.
Rericha, R., Horak, M., 1967. Determination of the degree of branching in alkanes by
infrared spectroscopy. I. Resolution of overlapping absorption bands in the 3000-
2900 cm-1 region. Collect. Czech. Chem. Commun. 32, 1125–1136. http://dx.doi.
org/10.1135/cccc19671125.
Rericha, R., Horak, M., 1968. Determination of the degree of branching in alkanes by
infrared spectroscopy. III. Analytical application. Collect. Czech. Chem. Commun. 33,
496–505. http://dx.doi.org/10.1135/cccc19680496.
Rule, G.S., Hitchens, T.K., 2006. Fundamentals of Protein NMR Spectroscopy. Springer,
Dordrecht ISBN 1-4020-3500-4.
Sanchez-Minero, F., Ancheyta, J., Silva-Oliver, G., Flores-Valle, S., 2013. Predicting SARA
composition of crude oil by means of NMR. Fuel 110, 318–321. http://dx.doi.org/10.
1016/j.fuel.2012.10.027.
Smirnov, M.B., Vanyukova, N.A., 2014. Relations between the main structural-group
composition parameters of Western Siberia crude oils according to NMR data. Pet.
Chem. 54, 355–365. http://dx.doi.org/10.1134/S0965544114050090.
Tianguang, F., Jianxin, W., Jill, S.B., 2002. Evaluating crude oils by SARA analysis. In:
Society of Petroleum Engineers PE/DOE Improved Oil Recovery Symposium, 13–17
April, Tulsa, Oklahoma, http://dx.doi.org/10.2118/75228-MS.
Usachev, K.S., Filippov, A.V., Filippova, E.A., Antzutkin, O.N., Klochkov, V.V., 2013a.
Solution structures of Alzheimer's amyloid A13-23 peptide: NMR studies in solution
and in SDS. J. Mol. Struct. 1049, 436–440. http://dx.doi.org/10.1016/j.molstruc.
2013.06.043.
Usachev, K.S., Filippov, A.V., Antzutkin, O.N., Klochkov, V.V., 2013b. A combination of
the RDC method and NOESY NMR spectroscopy for structural determination of the
Alzheimer's amyloid Aβ10-35 peptide in solution and in SDS micelles. Eur. Biophys.
J. 42, 803–810. http://dx.doi.org/10.1007/s00249-013-0928-7.
Usachev, K., Yamaguchi, Y., Takamatsu, M., Pavlova, N., Klochkov, V., Kurbangalieva, A.,
Murase, T., Shimoda, T., Tanaka, K., 2017a. Simple Gd3+-Neu5: N Ac complexation
results in NMR chemical shift asymmetries of structurally equivalent complex-type N
-glycan branches. Analyst 142, 2897–2900. http://dx.doi.org/10.1039/c7an00817a.
Usachev, K.S., Kolosova, O.A., Klochkova, E.A., Yulmetov, A.R., Aganov, A.V., Klochkov,
V.V., 2017b. Oligomerization of the antimicrobial peptide Protegrin-5 in a mem-
brane-mimicking environment. Structural studies by high-resolution NMR spectro-
scopy. Eur. Biophys. J. 46, 293–300. http://dx.doi.org/10.1007/s00249-016-1167-5.
Van den bergh, W., 2011. The Effect of Ageing on the Fatigue and Healing Properties of
Bituminous Mortars. Wohrmann Print Service, Zutphen ISBN 978-90-8570-784-4.