Bansal - Structural Aspects of Asphaltenes by NMR & XRD & Spectroscopic Techniques, 2004

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Structural Aspects of Crude Oil Derived Asphaltenes

by NMR and XRD and Spectroscopic Techniques
a a a
V. Bansal , M. B. Patel & A. S. Sarpal
a
Indian Oil Corporation Ltd. , R & D Centre , Faridabad, Haryana, India
Published online: 15 Aug 2007.
To cite this article: V. Bansal , M. B. Patel & A. S. Sarpal (2004) Structural Aspects of Crude Oil Derived Asphaltenes by
NMR and XRD and Spectroscopic Techniques, Petroleum Science and Technology, 22:11-12, 1401-1426, DOI: 10.1081/
LFT-200027776
To link to this article: http://dx.doi.org/10.1081/LFT-200027776
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PETROLEUM SCIENCE AND TECHNOLOGY
Vol. 22, Nos. 11 & 12, pp. 1401–1426, 2004
Downloaded by [New York University] at 11:41 19 May 2015
Structural Aspects of Crude Oil Derived

Asphaltenes by NMR and XRD and
Spectroscopic Techniques
V. Bansal, M. B. Patel, and A. S. Sarpal*
Indian Oil Corporation Ltd., R & D Centre,

Faridabad, Haryana, India
ABSTRACT
Asphaltene samples obtained from crude processed at two Indian

refineries were characterized for chemical composition and structure
by nuclear magnetic resonance (NMR), X-ray diffractometry
(XRD), fluorescence spectroscopic techniques, and chromatographic
(column and GPC) techniques. Estimation of NMR average
structural parameters were obtained by combined 1H, NMR 13C,
NMR DEPT-45, and QUAT pulse sequence spectral editing
techniques. The macrostructure and crystalline parameters of these
samples were obtained by XRD. The nature of the functional groups
have been obtained by IR technique. A combined NMR and XRD
parameters were used to estimate the size of average aromatic
structural units. Asphaltenes from one of the crudes (ASP-A) was
*Correspondence: A. S. Sarpal, Indian Oil Corporation Ltd., R & D Centre,

Sector 13, Faridabad, Haryana, India; E-mail: sarpalas@iocrnd.stpn.soft.net.
1401
DOI: 10.1081/LPET-200027776 1091-6466 (Print); 1532-2459 (Online)

Copyright & 2004 by Marcel Dekker, Inc. www.dekker.com
ORDER REPRINTS
1402 Bansal, Patel, and Sarpal
found to be highly pericondensed, highly substituted, and higher

molecular size compared to ASP-B asphaltene molecules. The
number of aromatic sheets per unit sheets are 3.7 and 2.5 in the
sample ASP-A and ASP-B, respectively. Both the asphaltene
molecules in the samples have periodically and systematic arrange-
ment of aromatic sheets in the unit sheet. The number of aromatic
rings per unit sheet in ASP-A and ASP-B are 6.0 and 5.0,
respectively. The fluorescence spectral studies has also exhibited
max (the wavelength of maximum intensity) at 505 and 509 nm
confirming to pericondensed higher polycondensed aromatic ring
system in both the samples. The analysis of liquid chromatographic
fractions of these samples show that each sample is composed of

several polycondensed aromatic systems where unit sheet of ring sizes
vary from 1.8 to 6.3 with varying molecular sizes. These structural
parameters allowed a model structure of the asphaltenes to be
constructed.
Key Words: Asphaltenes; Crude oil; NMR; XRD; IR; GPC;

Fluorescence spectroscopy.
INTRODUCTION
The characterization of asphaltenes is still a big challenge for the

fossil fuel industry. Asphaltenes create many problems during oil
production and refining processes including catalytic cracking. They
increase the viscosity and reduce the flow of oil or even stop the flow.
Their undesired precipitation, high tendency to form coke, catalyst
deactivation, and poisoning are the major problems during exploration
and refining. However, development of procedures to overcome these
problems and the establishment of a unique method for better utilization
are highly dependent on recognition of the structure of asphaltenes.
Hence, the elucidation of molecular structure of petroleum asphaltenes is
becoming more and more important.
Since molecular properties of petroleum and its fractions depend on
various parameters, considerable work has been carried out on the basic
structrual units within petroleum. Detailed structural information have
been obtained on the asphaltenes derived from crude oils using
a combination of different instrumental techniques such as XRD,
NMR, IR, SEM, etc. (Dickie and Yen, 1969; Espinat and Ravey, 1993;
Ignasiak et al., 1979; Ravey and Espinat, 1988, 1990; Reerink, 1971,
1973; Sadeghi et al., 1986; Yen et al., 1961). The fluorescence spectro-
scopy has been primarily used to study the nature of polyaromatic
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Crude oil Derived Asphaltenes 1403
hydrocarbons in crude and crude derived products, particularly heavier

ends like vacuum gas oil (VGO), bitumen, and asphaltenes (Kershaw et
al., 2000; Stasiuk et al., 2000).
In order to better understand the physicochemical behavior of
asphaltenes, it is of interest to know more about their chemical structure.
The present investigations have been undertaken in order to gain
quantitative data on structural aspects of asphaltene derived from crude
oils and to examine the variations in asphaltene structures from source to
source. Two asphaltene samples derived from crude oils processed at
different Indian refineries were studied. The main objective of these
studies was to characterize the asphaltenes and to propose the probable

model structure based on the structural parameters obtained from
analytical techniques such as nuclear magnetic resonance (NMR), X-ray
diffraction (XRD) infrared spectroscopy (IR), and chromatographic
(liquid and GPC) of samples and their fractions. The samples were
further fractionated on a column packed with silica/neutral alumina. The
fractions were collected employing a newly developed solvent system;
which provided separation on the basis of polarity and varying molecular
weight. The average structural parameters such as aromaticty (fa), degree
of condensation (Cb) and substitution (Csub), average number of aromatic
rings per aromatic sheet (Ra) and total number of aromatic rings per unit
sheet (Rat), average chain length of alkyl substituents, etc., were obtained
by combined XRD and IH/13C multipulse NMR techniques. These
structural parameters have enabled us to propose an average structure of
asphaltene molecules.
EXPERIMENTAL
Samples
To perform this study, asphaltenes were isolated from two crude oils
processed at different Indian refineries, as per the standard procedure
(IP-143/90).
Open Column Chromatography
Silica of mesh 60–120:neutral alumina grade (3:1), dried at 125 C,

200 C for 5 and 8 h, respectively was used as adsorbent. A glass column
of i.d. 1.5 cm, l 5.50 was used and packing of adsorbent was done very
carefully in order to avoid formation of air channels in the column.
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Table 1. Elemental analysis of asphaltenes.
Metals (ppm) ASP-A ASP-B Elements (wt%) ASP-A ASP-B
V 384.0 387.0 C 84.6 83.2

Ni 131.0 106.0 H 7.2 7.5
Na 145.0 66.0 N 1.0 1.0
Fe 37.0 112.0 S 6.6 7.3
Al <10.0 16.0 O 0.6 1.0
Ca <10.0 20.0
Cr <10.0 <10.0
Cu <10.0 <10.0
Zn <10.0 21.0
Molecular formulae: ASP-A ¼ C188 H192 N2 S5.4 O; ASP-B ¼ C110 H120 N S3.7 O.
The details of solvents selected for elution have been given in Table 1.
Benzene was selected as one of the solvents for elution, but for further
separations, dichloromethane (DCM) was used instead of benzene due to
its carcinogenicity.
Gel Permeation Chromatography
Gel permeation chromatography of the samples were recorded on

Waters 600 using a UV and Refractive Index Detector. P L Gel 5 m Mixed
D column of a length of 60 cm with exclusion limit up to 4,00,000 was
selected. The column was calibrated using polystyrene standards of
molecular weights 590,000, 207,000, 76,000, 22,000, 7000, and 1320.
Under the optimized conditions, the sample as such and its column
fractions were subjected to GPC. All samples were dissolved in THF and
filtered before injecting into the column. The flow rate of 1.0 mL per min
was maintained throughout the analysis. A calibration curve between
molecular weight and retention time was constructed. From the
calibration plot and retention time, the molecular weights (Mn, Mw,
Mp, and DP) have been automatically calculated from built-in software.
Analytical Procedure
The asphaltenes and their fractions were then characterized by using

following analytical techniques.
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X-ray Diffractometry
X-ray diffractograms of powdered asphaltane samples were obtained

with a high-power (12KW) X-ray diffractometer. The diffractometer
contained a rotating copper anode, a graphite monochromator, and a
scintillation counter. The diffraction patterns (2 ¼ 3–110 ) were
recorded at room temperature using Cu K radiation ( ¼ 1.54055 Å)
at a scanning speed of 1 deg min1 and a step size of 0.02 (2). Using a
software program, the recorded patterns were smoothed, background
subtracted, corrected for K 2 and deconvoluted; then peak position,
peak intensity, peak area, interplanar distance, and full width at half
maximum (FWHM) were calculated.
Nuclear Magnetic Resonance Spectroscopy

1
H and 13C n.m.r spectra were recorded on a Bruker ACP-300
FT-n.m.r spectrometer operating at 300 and 75.4 MHz, respectively. The
sample solutions were prepared in chloroform-d; tetramethysilane (TMS)
was used as an internal standard. Quantitative 13C n.m.r spectra were
recorded by adding a relaxation agent, chromium tris-acetylacetonate
[Cr(acac)3, 0.2 M], in the inverse gated condition (12–16) DEPT-13C-n.m.r
spectra were recorded by using the pulse sequence of Doddrel et al. (1982)
and Aue et al. (1976). The quart pulse sequence was used to estimate
quaternary carbons (Bendall et al., 1982).
Infrared Spectroscopy
The IR spectral analysis of all asphaltenes was carried out in CHCL3

solution.
Elemental Analysis
The C, H, and N content of these asphaltenes were estimated by an

elemental analyzer. Sulfur content was estimated by XRF spectrometry.
Other elements such as V and Ni were analyzed by ICAP-AES. The
results of elemental analysis are presented in Table 1.
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Fluorescence Spectroscopy
Fluorescence spectra are recorded at room temperature in UV grade

chloroform using Hitachi F 4500 spectrometer. A 150 W Xenon arc lamp
is used as an extended photomultiplier take having spectral response from
200 to 900 nm. The excitation and emission slits were kept at 2.5/2.5 nm
for all the spectra. Shutter control were also applied for the spectra. For
synchronous recording a value of 3 nm is used.
RESULTS AND DISCUSSION
The 1H and 13C-NMR spectra of asphaltene samples ASP-A and

ASP-B are given in Figs. 1 and 2, respectively. The regions corresponding
to aromatic hydrogen and carbons: -substituents on aromatic, saturate
hydrogens, and carbons are marked in their respective spectra. The
assignment of signals in the 1H and 13C-NMR spectra have been made
according to our earlier work (Christopher et al., 1996). The definition of
symbols used for structural parameters are given in Table 2.
1
H-NMR Spectral Analysis
The percentages of hydrogens and carbons corresponding to

aromatic and saturate parts are given in the Table 3. The hydrogen
distribution data shows that sample ASP-A contains a higher number of
bridged carbons or fused aromatic rings than the sample ASP-B as the
percentage of aromatic hydrogens (Ha) is lower as compared to ASP-B.
Since the percentage of H (i.e., substituted saturated group - to
aromatics ring) are the same for both the samples, this gives indication of
similar pattern of substitution on the aromatic ring. The 1H-NMR
spectral analysis has also shown the presence of -CH3 substituents on
the aromatic rings in both the samples. The percentage of -CH3 are
higher in case of ASP-A compared to ASP-B. These observations have
been further confirmed by 13C-NMR spectral analysis.
13
C-NMR Spectral Analysis
The carbon type compositional and structural parameter data as

estimated from the quantitative 1H and 13C-NMR spectra is given in
the Tables 3–5. The method of estimation of these parameters has been
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ASP-B
Hβ
H Hχ
Hα
ASP-A
Figure 1. 300 MHz 1H-NMR spectra of ASP-A and ASP-B.
13
Figure 2. 75.4 MHz proton decoupled C-NMR and spectra of ASP-A and
ASP-B.
described in our earlier published work (Christopher et al., 1996). The

direct quantitative estimation of bridged (Cb), substituted (Csub), and
protonated aromatic carbons (Cah) of average aromatic sheet have
also been estimated by the use of DEPT-45 and QUAT-pulse sequences.
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Table 2. Average structural parameters used for model structures.
Parameters Definitions
fa Aromaticity factor or fraction of aromatic carbons

Ca ¼ 100 fa Percentage of aromatic carbons
H, H Percentage hydrogens of saturated groups and
to aromatic rings
H Percentage of terminal methyl hydrogens
CNP Number of straight chain paraffinic carbons
R2 Average number of carbons per straight chain paraffin
on naphthenic rings
Ca, Cp, Cn Number of aromatic, paraffinic, and naphthenic carbons,
respectively, per unit sheet.
C , H Total number of carbon and hydrogen atoms per unit sheet
Hs, Cs Number of saturated hydrogens and carbons per unit sheet
(H/C)ar, (H/C)sat Hydrogen/carbon atomic ratio of aromatics or saturates
(H/C)T Total hydrogen/carbon ratio per average molecule
MF Molecular formula
M Molecular wt of a unit sheet
Cb Number of bridgehead carbons per unit sheet
Cib Number of internal bridged aromatic carbons per unit sheet
Csub Number of substituted aromatic carbons
Cah Number of protonated aromatic carbons
Cper Number of peripheral aromatic carbons
R3 Average carbon chain length of substituents on aromatic ring
Csub/Cper Degree of aromatic substitution
CbCa Degree of aromatic condensation
Cper/Ca Size of aromatic sheets
Cx Aromatic atoms attached to hetero atoms (O, N, S)
Ra Average number of aromatic rings per aromatic sheet
Rat Total number of aromatic rings per unit sheet
The pulse delay time (D2) for these experiments was optimized on
1-methylnaphthenes taken as a reference compound. It has been observed
that when the D2 was between 0.003 to 0.0035 s, a reasonable suppression
of the protonated signals in the 13C-QUAT spectrum could be achieved.
Similarly 13C DEPT-45 experiments provided consistent results of
protonated carbons in the optimized D2 range. The results obtained on
asphaltene samples are given in Table 3 along with those indirect
methods (Bendall et al., 1982). There is a very good agreement among
both the methods. The sample ASP-A contains higher number of
aromatic carbons (51.7%) compared to sample ASP-B (47.0%). The data
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13
Table 3. Average structural parameters by C & 1H-NMR
analysis.
Parameters ASP-A ASP-B
Ha 7.9 9.7
H 11.5 11.0
H 64.6 60.0
H 16.0 19.3
Ca 51.7 47.0
Cp 33.2 34.9
Cn 15.1 18.1
-CH3 9.5 12.0
t-CH3 3.3 4.6
b-CH3 6.2 7.4
Cb 31.1 (31.8)a 38.9 (31.6)a
Csub 5.8 5.4
Cah 10.2 (9.7)3 7.4 (7.9)b
a
¼ 13C QUAT.
b
¼ DEPT-45Experiment.
in a Table 4 shows that the average length of the alkyl substituents (R3),
other than CH3 on the aromatic rings, is the same (9.6) for both the
samples. However, the alkyl chain is more branched in ASP-B than in
ASP-A. This is indicative of a higher percentage of branched methyl in
sample ASP-B (7.4%) compared to sample ASP-A (6.2%). The total
number of branched and terminal methyls are also higher in ASP-B
(12.0%) compared to ASP-A (9.5%). The naphthenic carbons are also
slightly higher in ASP-B (18.1%) compared to ASP-A (15.1%). The
combined 13C and 1H-NMR spectral analysis show that aromatic rings
carbons are less substituted (5.6% average) in both the cases. This is also
evident from the presence of more peripheral protonated carbons in both
the samples.
Structural Parameters
The parameters in terms of absolute numbers of hydrogen and

carbon as given in Table 4 have been estimated by the procedure
described elsewhere (Christopher et al., 1996). These parameters reflect
the clear status regarding the nature of the aromatic rings with respect to
degree of substitution, condensation pattern (para or keta), nature of
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Table 4. Absolute no. of carbon and hydrogen atoms per unit

sheet of asphaltenes by 1H and 13C-NMR spectroscopy.
Ca 207.3 115.2

H 126.6 137.3
Ha 10.0 13.3
Hs 116.6 124.0
Ca 107.2 54.2
Cp 68.9 40.3
Cn 31.2 20.7

Cah 10.0 13.3
CSUB 11.2 6.7
Cb 86.0 34.2
Cib 70.8 20.2
MF C207H127 C115H137
M Wt 2,614 1,519
Table 5. Average structural parameters by 13C and 1H-NMR

analysis.
fa 0.51 0.47
Cper/Ca 0.25 0.33
Csub/Cper() 0.42 0.36
Cb/Ca() 0.80 0.63
Rat 44.0 18.1
R2 ,R3 9.6 9.6
R1 C1– C2 C1
(H/C)ar 0.09 0.25
(H/C)sat 2.0 2.03
(H/C)T 0.61 1.2
Cau 29.0 23.0
N 4.7 4.7
Ra 6.0 5.0
alkyl substituents, molecular size, and weight of asphaltene molecules.

The data in the Table 4 clearly indicates that size of aromatic moiety
is much larger in case of asphaltene ASP-A (C ¼ 207, M ¼ 2614)
compared to ASP-B (C ¼ 115, M ¼ 1519). The system is highly keta
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Figure 3. Deconvoluted XRD pattern of ASP-A.
condensed in ASP-A compared to ASP-B molecules. This is indicated by

a less percentage of protonated aromatic carbon (10.0%) and higher
degree of condensation (80.0%) in ASP-A sample. The degree of
aromatic substitution, is a higher income of ASP-A (42%) compared to
ASP-B (36%).
XRD Studies
The XRD pattern of these samples are given in Fig. 3. The XRD
pattern of the asphaltenes exhibit characteristics bands at d ¼ 4.8 Å
(, gamma Band), 3.5 Å (002 band), 2.1 Å (10 band), and 1.2 Å (11 band).
The peak position in the XRD pattern provide information about
distance (d) between the two aliphatic (, gamma band) and (dm) the
distance between two aromatic sheets (002 band). The average number of
aromatic sheets Mc were calculated using d and cluster diameter Lc
(Table 6) as described in our earlier work (Bendall et al., 1982). Similarly
the size of the aromatic sheet (La) and average number of aromatic rings
in the aromatic sheet (Ra) were calculated using the equations from
Stasiuk et al. (2002) or Kershaw et al. (2000) bands using equations given
in the reference (Christopher et al., 1996). All these parameters are
presented in the Table 6, which clearly indicates a higher number of
condensed aromatic rings in sample ASP-A (6.0) compared to 5.0 in the
ASP-B samples. Since the XRD pattern of these samples exhibit -band,
the aromatic sheets are arranged periodically and systematically. Both the
asphaltene molecule have identical d and dm. This implies to posses
similar stacking of asphaltene molecules in the system; although their
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Table 6. Structural data obtained from XRD-pattern.
Distance between two aliphatic chains, d (Å) 4.40 4.37

Distance between two aromatic sheets, dm (Å) 3.15 3.56
Cluster diamter, Lc (Å) 23.7 25.4
Average number of aromatic sheets, Mc 6.7 7.1
Size of aromatic sheets, La (Å) 16.6 13.1
Aromatic carbon atoms per atomic structure unit, Caua 29.1 23.3
Average number of aromatic rings per aromatic sheet, Ra 6.2 4.9
sizes are different and contains same number of aromatic units per unit
sheet of asphaltene molecules.
Flourescence Spectroscopy
The emission spectra (ex ¼ 400 nm) and synchronous spectra

( ¼ 9 nm) of samples ASP-A and ASP-B are given in the Figs. 4
and 5, respectively. The spectra were recorded at a very low concentra-
tion of 108 ppm in order to eliminate nonradiative emission processes due
to intermolecular interaction among the polynuclear aromatic molecules
(Alexander et al., 1980). The spectra of both the samples showed a similar
fluorescence pattern with board maxima except the intensity at max (the
wave length of maximum intensity) which shows a higher value for
ASP-A compared to ASP-B. The max in the emission fluorescence
spectra has been found to be the same viz 505 and 509 nm for ASP-A and
ASP-B, respectively. The maximum intensity at max is quite high for
sample ASP-A (10.0) compared to ASP-B (5.0). The synchronous
fluorescence spectra at ¼ 9 nm has also shown the similar results
(Fig. 5). The fluorescence spectral studies has revealed the following facts
about the nature of aromatic condensed system.
1. The asphaltene molecules have a similar pattern of condensation

of aromatic rings in both the samples. This is evidenced by the
same value of max and also supported by the combined NMR
and XRD studies where the average number of condensed
aromatic rings per aromatic sheet have been determined to be
6 and 5, respectively in ASP-A and ASP-B (Table 5).
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Figure 4. Deconvoluted XRD pattern of ASP-B.
Figure 5. GPC of asphaltene ASP-A and their fractions.
2. The appearance of a very broad maxima in both the cases are

indicative of a broad distribution of polyaromatic condensed
system with varying sizes of the aromatic sheet in a unit sheet of
asphaltene molecules (Stasiuk et al., 2000). This has been further
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Figure 6. Average model structure of fractions of ASP-A and ASP-B samples

and their fractions.
supported by the higher value of polydispersity of GPC profile

(2.5 and 3.5 in ASP-A and ASP-B, respectively).
3. The higher fluorescence intensity of maxima in the case
of sample ASP-A (10.0) compared to sample ASP-B (5.0) is in
agreement with the NMR data given in Tables 4 and 5. The total
number of condensed aromatic rings in a unit sheet of asphaltene
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molecule (RT) are 44 and 18 in samples ASP-A and ASP-B,

respectively. Since the size of the aromatic sheets are quite
large it would have been expected to achieve still higher
fluorescence. The moderate fluorescence in both the samples
has been attributed to higher degree of aromatic substitution as
0.42 and 0.36 in sample ASP-A and ASP-B, respectively
(Alexander et al., 1980).
4. The polyaromatic rings are keta-condensed like pyrene or a
similar higher aromatic ring system. This information is revealed
by the max values, broad maxima and more dispersion in
the fluorescence spectra in both the cases. The system-like

anthracene, naphthalene, binaphthalene, and bianthracene,
which are paracondensed systems, exhibit fluorescence in the
region of 320–420 nm with the max around 380–400 nm (Tueker
et al., 1994). However, the higher polycondensed system like
coronylene and dicoronylene give fluorescence maxima around
506 nm. From the above discussion it has been concluded that
the structural parameters of two samples, as elucidated by the
combined NMR and XRD studies, are in agreement and
supported by the fluorescence spectral studies.
Model Structure of Asphaltenes
In order to derive the model structure of asphaltenes, some more

useful structural parameters have been estimated from the combined
NMR and XRD data (Table 5), as explained elsewhere (Christopher
et al., 1996). The structural parameters given in the Tables 2–6 have
been used to propose a hypothetical average model structure for these
samples as shown in Fig. 4. The hetro atoms N, S, and O have also been
incorporated in the form of functional groups as indicated by their
IR analyses. The IR spectral analyses has indicated a band due to
phenolic -OH at 3422 cm1 in both the samples, which has been
incorporated in the model structures. Since no intense signals due to
sulphoxide linkages were observed in the IR spectra in the region of 900
to 1300 cm1, the S-atom has been incorporated in the naphthenic rings.
The structural parameters such as (H/C)ar, Cah, and Cper/Ca provide
a fair degree of justification for the proposed model structures. The
Cper/Ca which represents the size of the aromatic sheet is the lower for
ASP-A (0.25) compared to ASP-B (0.33). The lower value is the
indication of a higher number of rings and size of the aromatic sheet,
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Table 7. Open column chromatographic data.
ASP-A ASP-B
Frac. Mobile phase Recovery (%) Mobile phase Recovery (%)
F1 Heptane:Benzene 36.0 Heptane:DCM 41.3

(60:40) (60:40)
F2 Heptane:Benzene 20.0 Heptane:DCM 25.0
(30:70) (30:70)
F3 Benzene 12.0 DCM 24.5
F4 Benzene:CHCl3 24.0 DCM:CHCl3 8.3

(50:50) (50:50)
F5 CHCl3 2.0 CHCl3 0.5
which is the case with sample ASP-A. Similarly (H/C)ar determines the
size of the aromatic rings condensed to each other. Since it is lower for
ASP-A (0.09), this molecule of asphaltene should contain a higher
number of aromatic rings with a larger size. This is also reflected by the
parameter La estimated by XRD data. The model structure contains a
less number of naphthenic rings. This is further supported by the higher
H/C ratio (2.0) for both the samples.
ANALYSIS OF FRACTIONS
Since the asphaltene molecules are composed of different condensed

PAH with varying molecular sizes, as was evident from the GPC profile
of the sample as such, a novel separation scheme has been developed to
obtain subfractions employing adsorption chromatography (Demirbas,
2002; Hirsch et al., 1972), Table 7. For the purpose of comparative study
of asphaltenes in terms of their structural variation and molecular weight
distribution, all fractions collected so far have been subjected to GPC
analysis for molecular weight determination, IR for functional groups,
NMR and XRD for carbon type analysis and structural parameters.
GPC Analysis
Gel permeation chromatography analyses data of the samples as

such (ASP-A and ASP-B) and their column fractions have been given in
Table 8, indicating that molecular weights (Mn, Mp, and Mw) of fractions
ORDER REPRINTS
Table 8. GPC data of samples and column fractions.
ASP-A ASP-B
Fraction Mn Mp Mw DP Mn Mp Mw DP
As such 2,626 9,530 6,006 2.3 1,900 8,455 6,170 3.2

F1 1,766 6,238 4,395 2.5 1,600 7,700 6,100 3.8
F2 1,525 5,576 4,044 2.6 1,300 7,100 5,200 4.0
F3 1,312 3,338 2,991 2.3 1,200 2,600 3,400 2.8
F4 1,407 3,616 3,363 2.4 1,900 4,800 5,400 2.8
decreases as we increase the polarity of the solvent (i.e., less polar

constituents of ASP-A sample have high molecular weight and more
polar constituents have low molecular weight, Table 5).
Gel permeation chromatography profile of first fraction (F1) of ASP-
B sample shows two distinct peaks at 16.5 and 14.7 min, respectively,
indicating the presence of two different molecular weight species in this
fraction; the low molecular weight species being due to maltenes. Profile
of second fraction (F2) shows an intense peak with skewedness in low
molecular weight region and that of fraction F3 shows highly dispersed
band. The profile of fraction F4 is similar to that of fraction F2 but have
less skewedness. The chromatograms show a shift to low molecular
weight region as the polarity of solvent is increased, which indicates that
high molecular weight species are less polar in nature. GPC analysis show
that more polar constituents have less molecular weight, Table 8.
X-ray Studies
The various parameters obtained from deconvoluted XRD patterns

for different fractions are given in Table 9, which clearly indicates that a
higher number of condensed aromatic rings in F2 (6.0) compared to 5.0
in F4. Aromatic sheets are arranged periodically and systematically.
Fractions F2 and F4 both have the same d and dm values, which implies a
similar stacking of asphaltene molecules in the system though their sizes
are different.
In deconvoluted XRD pattern of fractions of ASP-A, the gamma
band at d ¼ 4.5 due to aliphatic structure and 002 band at d ¼ 3.5 due to
aromatic molecules have been well separated in fractions F2 and F4
compared to F1 and F3. Both the peaks have been found to merge
together and appear as a single peak in F1 and F3. This observation
ORDER REPRINTS
Table 9. Structural data obtained from XRD pattern.
Parameters ASP-A F1 F2 F4
d (Å) 4.40 4.10 4.30 4.32

dm (Å) 3.15 3.53 3.54 3.52
Lc (Å) 23.7 27.52 26.25 31.24
Mc 6.7 7.79 7.41 8.87
La(Å) 16.6 — 14.22 12.91
Caua 29.1 — 25.1 23.0
Ra 6.2 — 5.33 4.84
d (Å) ¼ Distance between two aliphatic chains.

dm(Å) ¼ Distance between two aromatic sheets.
Lc (Å) ¼ Cluster diamter, Mc ¼ Average number of aromatic sheets.
La(Å) ¼ Size of aromatic sheets.
Caua ¼ Aromatic carbon atoms per atomic structure unit.
Ra ¼ Average number of aromatic rings per aromatic sheet.
indicates that in the case of F2 and F4 fractions, crystallite size is higher

(i.e., higher degree of crystallinity) for both aliphatic and aromatic sheets
compared to F1. In the case of F3, both peaks merge together and give a
single peak in between, indicating that not only their crystallite size is
smaller, but they also are oriented randomly.
1
H/13C-NMR Spectral Analysis
The average structural parameters have been derived from

1
H/13C-NMR spectra of the samples as such and their subfractions by
the procedure described elsewhere (Christopher et al., 1996). The carbon
type compositional data and structural parameters have been given in
Tables 10–13. The direct quantitative estimation of bridged (Cb),
substituted (Csub), and protonated carbons (Cah) of average aromatic
sheet have also been done by the use of 13C DEPT-45, DEPT-135,
and Quat-pulse sequences. There is good agreement between direct
quantitative estimation with that of an indirect method (Christopher,
1996).
The spectral analysis of the fractions of the ASP-A sample reveals
the following facts about their nature with regard to carbon type, the
structural parameters.
ORDER REPRINTS
Table 10. Average structural parameters by 1H/13C-NMR spectral analysis.
Parameter ASP-A F1 F2 F3 F4
C 207.3 56.0 170.3 54.3 122.5

H 126.6 56.8 125.3 61.2 112.6
Ha 10.0 10.2 17.5 11.0 15.5
Hs 116.6 46.6 107.7 50.2 97.1
Ca 107.2 28.9 108.2 27.0 69.0
C s 100.1 27.1 62.1 27.3 53.5
Cp 68.9 16.7 38.0 19.7 35.2
Cn Cn 31.2 10.4 24.0 7.5 18.3

Cah 10.0 10.2 17.5 11.0 15.5
Csub 11.2 3.8 9.9 2.5 6.3
Cb 86.0 15.0 80.8 13.5 47.2
Cib 70.8 7.0 59.0 6.0 31.3
Cper 14.0 27.4 13.5 21.8
fa 0.51 0.51 0.63 0.49 0.56
Cper/Ca 0.25 0.48 0.25 0.50 0.31
Csub/Cper() 0.42 0.27 0.36 0.20 0.30
Cb/Ca() 0.80 0.52 0.75 0.50 0.68
Rat 44.0 8.5 41.4 7.7 24.6
CNP — 17.6 36.6 17.0 26.1
Cau 29.0 — 25.1 — 23.0
N 3.7 — 4.3 — 3.0
Ra 6.2 — 5.3 — 4.84
MF C207H127 C56H57 C170H125 C54H61 C122H112
M.wt. of one sheet 2,611 729 2,165 709 1,576
Total M.wt. 6,006 4,395 4,044 2,991 3,363
Number of unit sheets 2.3 6.3 1.86 4.2 2.1
. The percentage of Ha [i.e., aromatic hydrogen (14–17.9%)] is

higher in all the fractions compared to the sample, as such (7.9%)
indicating less substituted ring aromatic pattern. This is further
supported by the degree substitution (), which is sufficiently low
(0.2–0.36) as compared to a sample as such (0.42). The higher
value of (Cper/Ca) and (H/C) compared to the sample as such give
strong evidence of the presence of a higher number of protons in
the aromatic systems (i.e., system is less substituted).
. The degree of condensation () has also shown a decreasing trend
for fractions F1–F4 (0.52–0.75) compared to sample as such (0.8).
This shows a decrease in the average size of the aromatic ring
sheet per unit sheet of the sample.
ORDER REPRINTS
13
Table 11. Average structural parameters by C and 1H NMR analysis of
ASP-A.
Parameters ASP-A as such F1 F2 F3 F4
Ha (%) 7.9 17.9 14.0 17.9 13.7

H (%) 11.5 13.3 15.9 8.2 11.2
H (%) 64.6 53.3 53.4 58.4 52.4
H (%) 16.0 15.4 16.3 15.4 22.5
Ca (%) 51.7 51.7 63.5 49.7 56.3
Cp (%) 33.2 29.8 22.3 36.4 28.7
Cn (%) 15.1 18.5 14.1 13.8 14.9

T-CH3 (%) 9.5 7.7 5.9 7.2 9.1
t-CH3 (%) 3.3 3.8 2.6 3.9 4.5
b-CH3 (%) 6.2 3.8 3.3 3.4 4.6
Table 12. Average structural parameters by combined NMR-XRD analysis of

ASP-A.
Parameters ASP-A as such F1 F2 F3 F4
fa 0.51 0.51 0.63 0.49 0.56

Cper/Ca 0.25 0.48 0.25 0.50 0.31
Csub/Cper() 0.42 0.27 0.36 0.20 0.30
Cb/Ca() 0.80 0.52 0.75 0.50 0.68
Rat 44.0 8.5 41.4 7.7 24.6
R1
R2 9.6 10.8 10.4 11.2 8.7
(H/C)ar 0.09 0.35 0.16 0.41 0.22
(H/C)sat 2.0 1.72 1.73 1.84 1.81
(H/C)Tot 0.61 1.0 0.7 1.1 0.9
CNP 17.6 36.6 17.0 26.1
Cau 29.0 25.1 23.0
N 3.7 4.3 3.0
Ra 6.2 5.3 4.84
(T-CH3) 19.7 4.3 10.0 3.9 11.1
(t-CH3) 6.8 2.1 4.4 2.1 5.5
(b-CH3) 12.8 2.1 5.6 1.8 5.6
ORDER REPRINTS
13
Table 13. Average structural parameters by C and 1H NMR analysis of
ASP-B.
Parameter ASP-B as such F2 F3 F4 F5
Ha (%) 9.7 13.8 14.6 14.9 16.3

H (%) 11.0 15.0 11.9 13.4 14.9
H (%) 60.0 52.0 49.5 48.2 49.0
H (%) 19.3 19.1 23.8 23.4 20.4
Csub/Cper() 0.36 0.35 0.29 0.31 0.31
. The fractions F2, F4 and F1, F3 are identical in nature with

regard to ring size and substitution pattern.
. The nearly same values of the length of average alkyl substituents
(8.7–11.2) are indicative of the similar paraffinic environment.
It has also been confirmed by XRD analysis, which has shown a
less crowd of alkyl chain in the overall molecular environment of
the sample.
. From the Table 10, it is clear that fraction F2 contains the highest
number of aromatic carbons (108) followed by F4, F1, and F3
(69, 29, and 27, respectively). Average length (R2) of the alkyl
substituents other than CH3 on aromatic rings is nearly the same
(10.8 and 11.2) for F1 and F3. R2 value for F2 and F4 is 10.4 and
8.7, respectively. However, alkyl chain of F4 is more branched
than that of F1, F2, and F3. There is more or less equal
distribution of branched and terminal methyl carbons on the alkyl
substituents.
. Percentage of naphthenic carbons is more in F1 and nearly same
in F2 (14.1%), F3 (13.8%), and F4 (14.9%), while absolute
number of naphthenic carbons is more in F2 (24.0). Total number
of carbons is more in F2 (170.3). This fraction also contains the
highest number of protons. Total number of C and H is least and
nearly same for F1 (56.0) and F3 (54.3). This indicates that
fractions F2 and F4 contain sheets of bigger size and high
molecular weight while F1and F3 contain smaller sheets.
. Degree of condensation data shows that F2 is highly condensed
(0.75) followed by F4 (0.68). F1 and F3 are comparatively less
condensed (0.52 and 0.50). High percentage of aromatic protons
in F1 and F3 and comparatively less percentage of aromatic
protons in F2 and F4 also support this fact. Higher value of
ORDER REPRINTS
(H/C)ar for F3 (0.41) also shows that F3 is less substituted and less
condensed. Percentage of straight chain paraffinic carbons is
higher for F1 and F3 (31% each) as compared to those for F2 and
F4 (21% each).
The percentage of aromatic hydrogens Ha (13.8–16.3%), is higher in

all the fractions of ASP-B sample as compared to sample as such (9.7%),
indicating less substituted ring aromatic pattern. This is further
supported by degree of substitution () which is low for fractions
(0.29–0.35) as compared to sample as such (0.36) (Table 13).
IR Spectral Analysis
Infrared spectral analysis of the samples ASP-A, ASP-B, and their

column fractions shows the presence of oxygen functionality at
1734 cm1 (ester), 1648 cm1 (conjugated carbonyl), and 1700 cm1
(acid). Relative abundance of C¼O has been estimated as follows:
ðI1735 þ I1700 þ I1650 Þ

Relative Abundance ðC ¼ OÞ ¼
ðI1735 þ I1700 þ I1650 þ I1600 Þ
where I1735, I1700, I1650, and I1600 are the intensities of the signals at 1735,
1700, 1650, and 1600 cm1 corresponding to ester, ketone/aldehyde, acid,
conjugated C¼O, and C¼C. The IR spectral data shows that the relative
abundance (C¼O) of the ASP-A, ASP-B samples as such and their
column fractions increases (0.436 to 0.685) and (0.55 to 0.68),
respectively, on increasing the polarity of solvent (Tables 14 and 15).
Table 14. Relative abundance of C¼O in ASP-A and its fractions from
IR analysis.
Relative
Fraction Intensity at Intensity at Intensity at Intensity at abundance
number 1,735 cm1 1,700 cm1 1,650 cm1 1,600 cm1 of C¼O
ASP-A as such 0.000 0.003 0.028 0.046 0.402

F1 0.004 0.003 0.017 0.031 0.436
F2 0.017 0.010 0.015 0.041 0.506
F3 0.016 0.004 0.012 0.016 0.666
F4 0.089 0.091 0.112 0.134 0.685
ORDER REPRINTS
Table 15. Relative abundance of C¼O in ASP-B and its fractions from IR
analysis.
Relative
Fraction Intensity at Intensity at Intensity at Intensity at abundance
number 1,735 cm1 1,700 cm1 1,650 cm1 1,600 cm1 of C¼O
ASP-B as such 0.014 0.032 0.030 0.082 0.48

F1 0.005 0.005 0.006 0.013 0.55
F2 0.005 0.017 0.021 0.031 0.58
F3 0.078 0.041 0.027 0.072 0.67
F4 0.099 0.099 0.104 0.139 0.68

F5 0.029 0.050 0.037 0.093 0.55
From the NMR, IR, GPC, XRD, and Flourescence spectral analysis,
it is quite apparent that sample ASP-A is composed of a large number of
aromatic hydrocarbon systems having broad distribution of molecular
weight and different fused polyring condensation systems with varying
degree of substitution pattern. The degree of the presence of heteroatoms
(S, N, and O) functionality in the polycondensed system is also dependent
upon the polarity of fractions from F1–F4. As the polarity of eluting
solvent is increased from F1 to F4, the regular increase in the oxygen
containing functional group is experienced. There is a gradual fall in
the molecular weight level as the polarity of the solvent is increased.
Thus, more polar solvent elutes components of higher polar aromatic
system with low molecular weight.
Average Model Structure
Based on the average structural parameters estimated by the 1H/13C

NMR spectral analysis and XRD pattern with respect to average number
of aromatic sheets and average number of aromatic rings in each
aromatic sheet, the average model structure of each fraction and sample
as such have been proposed. These structures incorporate all the different
types of carbons and satisfy structural parameters as given in the Tables
10–15.
The fraction F1 and F3 of ASP-A contained 56 and 54.3 absolute
number of carbons per aromatic unit sheet including the substituent
carbons. The number of condensed aromatic rings per unit sheet are 8.5
and 7.7 in these fractions, respectively. The structural parameters
such as (H/C)ar(0.35, 0.41), Cah (10.2, 11.0), (Cb/Ca) (0.52, 0.50), and
ORDER REPRINTS
Cper/Ca)(0.48, 0.5) are also indicative of polycondensed system containing

a less number of aromatic rings in F1 and F3 fractions. Total number of
unit sheet per molecule of asphaltene has been estimated to be 6.3 and 4.1
and the molecular weight (Mw) estimated by GPC are 4395 and 3363,
respectively in F1 and F3 fractions.
The fraction F2 of ASP-A contained the largest number of aromatic
rings (41.4) per unit sheet of the asphaltene and as per XRD pattern
analysis, there are 5.0 aromatic sheets per unit sheet. The number of unit
sheets per molecule of the asphaltene has been determined to be 1.86
(Mw ¼ 4044). Number of aromatic rings per unit aromatic sheet is 24.6 in
F4 fraction of ASP-A and there are 3 aromatic sheets per unit sheet as
estimated by XRD analysis. The number of unit sheets per mole of
asphaltene is 2.1. The number of unit sheets per mole of the asphaltene
molecule has been determined to be 2.1. The proposed model structures
for two fractions of ASP-A have been given in Fig. 1. The similar
observations have been made for ASP-B sample.
CONCLUSIONS
The direct determination of bridged head and substituted aromatic

carbons by QUAT and DEPT pulse sequence and those by the
methodology described in this paper are in agreement. The combined
NMR/IR/XRD studies revealed a higher size of unit sheet of sample
ASP-A compared to sample ASP-B. The Cper/Ca data from NMR
conform to the structure in which the number of aromatic rings are keta
condensed to each other through naphthenic rings. In both the samples,
there are 5.0 units of aromatic sheets per molecule. The number of
aromatic rings per sheet are 6.0 and 5.0, respectively for ASP-A and
ASP-B. The -CH3 substituents are present in both the cases. The
average length of substituents other than CH3 is 10.6 in both the cases.
There are an average of 9.6 and 3.5 number of alkyl substituents on
the condensed aromatic system per molecule of ASP-A and ASP-B,
respectively. The fluorescence spectral studies have also indicated higher
polyaromatic condensed system with high max value.
The combined NMR, IR, GPD, XRD, and Flourescence spectro-
scopic data shows that molecular structure of asphaltene sample ASP-A
is quite different from that of ASP-B in terms of polycondensed aromatic
systems and size of unit aromatic sheet. Data shows that the size of unit
sheet is smaller for ASP-B compared to ASP-A, as there are 3 aromatic
sheets in ASP-B as compared to 4 in ASP-A. Cper/Ca data from NMR
confirm to a structure where aromatic sheets are pericondensed to each
ORDER REPRINTS
other through naphthenic rings. ASP-A ( ¼ 4.2) is more substituted than

ASP-B ( ¼ 3.6) as revealed by degree of substitution. Both samples have
the same length of straight paraffinic chain.
Gel permeation chromatography analysis of samples has shown
broad molecular distribution and the distribution pattern is different for
the two samples. Molecular weights (Mp, Mn, and Mw) are nearly the
same for ASP-A and ASP-B, but molecular weight distribution is broader
for ASP-B (DP ¼ 3.2) compared to ASP-A (DP ¼ 2.3). IR spectra shows
the presence of oxygen functionalities, whereas sulfur functionalities are
not clearly visible. GPC and IR analysis indicate that high molecular
weight constituents are less polar in nature. The fluorescence spectral

studies have also indicated higher polyaromatic condensed system with
high max value. The model structures proposed are quite consistent with
average structural parameters obtained by NMR and XRD analysis.
REFERENCES
Alexander, R., Gray, M. D., Kagi, R. I., Woodhouse, G. W. (1980).

Chem. Geol. 30.
Aue, W. P., Bartholde, E., Ernst, R. R. (1976). J. Chem. Phys. 64:2229.
Bendall, M. R., Pegg, D. T., Doddrell, D. M., Johns, S. R., Willing, R. I.
(1982). J. Chem. Soc. Chem. Commun. 1138.
Christopher, J., Sarpal, A. S., Kapur, G. S., Krishna, A., Tyagi, B. R.,
Jain, M. C., Bhatnagar, A. K. (1996). Fuel 75(8):999–1008.
Demirbas, A. (2002). Pet. Sci. & Tech. 20(5&6):485–495.
Dickerson, E. M. (1985). Fuel 64:704.
Dickie, J. P., Yen, T. F. (1969). J. Colloid Interface Sci. 29:475.
Doddrel, D. M., Pegg, D. T., Bendall, M. R. (1982). J. Magn. Res. 48:323.
Espinat, D., Ravey, J. C. (1993). SPE-Oilfield Chem. proc of Int. Sym.
Soc. Pet. Eng. (New Orleans) 365–373.
Hirsch, D. E., Hopkins, R. L., Coleman, H. J., Cotton, F. O., Thompson,
C. J. (1972). Analytical Chemistry 44(6):915–919.
Ignasiak, T. M., Bimer, J., Samman, N., Monotogomery, O. P., Strausz,
D. S. (1979). Prepr-Am. Chem., Soc. Div. Pet. Chem. 24(4):1001.
Jewel, D. M., Weber, J. H., Bunger, J. W., Plancher, H., Lathan, D. R.
(1972). Anal. Chem. 44(8):1391–1395.
Kershaw, J. R., Sathe, C., Hayashi, J. I., Li, C., Chiba, T. (2000). Energy
& Fuels 14:476–482.
Ravey, J. C., Espinant, D. (1990). Prog. Colloid Polym. Sci. 81:127–130.
Ravey, J. C., Espinat, D., Ducouret, G. (1988). Fuel 67:1560–1567.
Reerink, H. (1971). Prepr-Am. Chem. Soc. Div. Pet. Chem. 16(1):D18.
ORDER REPRINTS
Reerink, H. (1973). Ind. Eng. Chem. Prod. Res. Dev. 12:82.

Sadeghi, M. A., Chilingarian, G. V., Yen, T. F. (1986). Energy Sources
8:99–123.
Stasiuk, L. D., Gentzies, T., Rahimi, P. (2000). Fuel 79:769–775.
Tueker, S. A., Griffin, S. M., Acree, W. E., Zander, M., Mitchell, R. H.
(1994). Applied Spectroscopy 48(4):458–464.
Yen, T. F., Erdmann, J. G., Pollacks, S. S. (1961). Anal. Chem.
33(11):1587–1594.
Received October 2, 2002

Accepted November 1, 2002

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Petroleum Science and Technology

Structural Aspects of Crude Oil Derived Asphaltenes

To link to this article: http://dx.doi.org/10.1081/LFT-200027776

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Structural Aspects of Crude Oil Derived

V. Bansal, M. B. Patel, and A. S. Sarpal*

Indian Oil Corporation Ltd., R & D Centre,

Asphaltene samples obtained from crude processed at two Indian

*Correspondence: A. S. Sarpal, Indian Oil Corporation Ltd., R & D Centre,

DOI: 10.1081/LPET-200027776 1091-6466 (Print); 1532-2459 (Online)

1402 Bansal, Patel, and Sarpal

found to be highly pericondensed, highly substituted, and higher

fractions of these samples show that each sample is composed of

Key Words: Asphaltenes; Crude oil; NMR; XRD; IR; GPC;

The characterization of asphaltenes is still a big challenge for the

Crude oil Derived Asphaltenes 1403

hydrocarbons in crude and crude derived products, particularly heavier

studies was to characterize the asphaltenes and to propose the probable

Open Column Chromatography

Silica of mesh 60–120:neutral alumina grade (3:1), dried at 125 C,

1404 Bansal, Patel, and Sarpal

Table 1. Elemental analysis of asphaltenes.

Metals (ppm) ASP-A ASP-B Elements (wt%) ASP-A ASP-B

V 384.0 387.0 C 84.6 83.2

Gel Permeation Chromatography

Gel permeation chromatography of the samples were recorded on

The asphaltenes and their fractions were then characterized by using

Crude oil Derived Asphaltenes 1405

X-ray diffractograms of powdered asphaltane samples were obtained

Nuclear Magnetic Resonance Spectroscopy

The IR spectral analysis of all asphaltenes was carried out in CHCL3

The C, H, and N content of these asphaltenes were estimated by an

1406 Bansal, Patel, and Sarpal

Fluorescence spectra are recorded at room temperature in UV grade

RESULTS AND DISCUSSION

The 1H and 13C-NMR spectra of asphaltene samples ASP-A and

The percentages of hydrogens and carbons corresponding to

The carbon type compositional and structural parameter data as

Crude oil Derived Asphaltenes 1407

Figure 1. 300 MHz 1H-NMR spectra of ASP-A and ASP-B.

described in our earlier published work (Christopher et al., 1996). The

1408 Bansal, Patel, and Sarpal

Table 2. Average structural parameters used for model structures.

fa Aromaticity factor or fraction of aromatic carbons

Crude oil Derived Asphaltenes 1409

Parameters ASP-A ASP-B

The parameters in terms of absolute numbers of hydrogen and

1410 Bansal, Patel, and Sarpal

Table 4. Absolute no. of carbon and hydrogen atoms per unit

Parameters ASP-A ASP-B

Ca 207.3 115.2

Cn 31.2 20.7

Table 5. Average structural parameters by 13C and 1H-NMR

Parameters ASP-A ASP-B

alkyl substituents, molecular size, and weight of asphaltene molecules.

Crude oil Derived Asphaltenes 1411

Figure 3. Deconvoluted XRD pattern of ASP-A.

condensed in ASP-A compared to ASP-B molecules. This is indicated by

1412 Bansal, Patel, and Sarpal

Table 6. Structural data obtained from XRD-pattern.

Parameters ASP-A ASP-B

other through naphthenic rings. ASP-A ( ¼ 4.2) is more substituted than