Petroleum Science and Technology

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Structural characterization of asphaltenes derived

from nigerian bitumen using the x-ray diffraction
technique

J. O. Akinnifesi, F. M. Adebiyi & K. F. Olafisan

To cite this article: J. O. Akinnifesi, F. M. Adebiyi & K. F. Olafisan (2017) Structural

characterization of asphaltenes derived from nigerian bitumen using the x-ray diffraction technique,
Petroleum Science and Technology, 35:16, 1667-1672, DOI: 10.1080/10916466.2017.1356849

To link to this article: https://doi.org/10.1080/10916466.2017.1356849

Published online: 14 Nov 2017.

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PETROLEUM SCIENCE AND TECHNOLOGY
, VOL. , NO. , –
https://doi.org/./..

Structural characterization of asphaltenes derived from nigerian

bitumen using the x-ray diffraction technique
J. O. Akinnifesia , F. M. Adebiyib , and K. F. Olafisana
a
Department of Physics and Engineering Physics, Obafemi Awolowo University, Ile-Ife, Nigeria; b Department of
Chemistry, Obafemi Awolowo University, Ile-Ife, Nigeria

ABSTRACT KEYWORDS
Petroleum asphaltenes consist of complex hydrocarbon molecules that pose asphaltene; bitumen; carbon
a marked difficulty in the production of crude oils. They tend to flocculate and aromaticity; structural
precipitate during oils refinery and this stimulates considerable interest in the characterization; x-ray
diffraction
elucidation of their molecular structure for improved processing. In this inves-
tigation, five bitumen samples obtained from oil sand outcrops at five localities
in Nigeria were used. These were treated with n-pentane that necessitates the
precipitation of asphaltene. The different asphaltene samples were analyzed
by the x-ray diffraction technique to obtain their various structural parameters.
The parameters were determined from the peaks of the gamma (γ ) band,
graphene (c = c) or (002) band and the (10) or (11) band in the diffraction spec-
tra of the respective samples. Slight variations in the distance between the
aliphatic chains and the distance between the aromatic sheets were observed
for three of the samples, while the remaining two presented significant varia-
tions in the structural parameters. Variations in the average number of carbon
atoms per aromatic units correspond to the variation in the size and number of
aromatic units and aliphatic chains. The variations consequently determined
the level of processing necessary to improve the heavy oil (bitumen).

1. Introduction
Crude oil is composed mainly of paraffinic and aromatic hydrocarbon molecules besides the presence of
sulphur. In addition to sulphur, oxygen and nitrogen are present in variable amounts (Speight 2001; Yasar
et al. 2001). Also, metallic traces of Nickel, Vernadium, Iron, and Copper may in general be included in
the composition (Simanzhenkov and Idem 2003). Vernadium is recognized in the world over as the most
abundant metallic constituent in petroleum, which causes negative side effects in the refining process
(Amorim et al. 2007). The location and age of an oil field significantly affect the chemical composition
and quality of crude oil. Heavy crude oils contain higher complex hydrocarbon molecules and metal
contents compared with lighter crude oil (Akmaz et al. 2011). Processing poses more difficulty for heavy
crude oil; hence, attention is concentrated largely on light crude oil reserve for exploitation, and this
tends to deplete more rapidly. The need therefore arises to explore the possibility of converting heavy
petroleum into more valuable products. To this effect, fractionating of the chemical structure of crude
oil is usually carried out by the specific mixing of compound types.
The saturate, aromatic, resins, and asphaltenes (SARA) technique is the most widely used. Speight
(2001), Klein et al. (2006), and Paratta-Martinez et al. (2008) have used the method to separate crude
oils into the major four fractions. They found that the saturate compounds are mostly aliphatic, while
the aromatic fraction consists of aromatic groups with aliphatic side chains, whereas resin is a heavier

CONTACT F. M. Adebiyi fmbiyi@oauife.edu.ng; biyi@yahoo.com Department of Chemistry, Obafemi Awolowo

University, Ile-Ife , Nigeria.
©  Taylor & Francis Group, LLC
1668 J. O. AKINNIFESI ET AL.

fraction than aromatic and saturate. Fan and Buckley (2002) found asphaltene to be insoluble in n-alkane
solvents and is the most complex fraction of crude oils. In general, higher asphaltene contents in crude oil
are known to be more problematic during refining operation (Ali et al. 1989; Gray 1994). The problems
arise from their tendency to flocculate and precipitate during processing. They cause dramatic reduc-
tion of oil flow or even blockage (Calemma et al. 2002). They thus produce severe drawbacks on the
account of their tendency to act as precursor of coke that deactivates catalysis and reduces the overall
rate of desulphurization during processing (Shen 2002). By definition, asphaltene is the insoluble part of
petroleum after the addition of aliphatic hydrocarbon solvents such as n-pentane and n-heptane, in the
volume ratio of at least 1 (oil): 40 (solvent) (ASTM 2006). They appear as dark brown to black friable
solids and have no definite melting point.
Several investigations have used a great variety of analytical techniques to examine the asphaltene
molecular structure. Elemental analysis determines the carbon, hydrogen, and oxygen content, while
nuclear magnetic resonance determines the distribution of hydrogen and carbon. Infrared and Fourier
transform infrared (FTIR) permit the determination of the relative abundances of some functional
groups, chiefly hydroxyl, carbonyl and adjacent aromatic CH groups in the fractions of crude oil
(Ali et al. 1989; Rudzinski et al. 2000; Aske et al. 2001; Buenrostro-Gonzalel et al. 2001; Adebiyi and
Thoss 2014; Adebiyi and Thoss 2015). FTIR has particularly been used to determine the presence
of carbonyl group in the resin and asplhatene fractions (Peratta- Martinez et al. 2008; Anderson et
al 2005). For the determination of molecular weight of fractions of crude oil, the gel permeation
chromatography and electro-spray ionization mass spectrometry have been used (Buenrostro-Gonzalel
et al. 2001; Akmaz et al. 2011). In another analytical development, Albari (2012) found that the shape
of boiling point distribution curve of a petroleum field is representative of the components within it.
When coupled with an appropriate mathematical model, this can be used to calculate the properties
of the petroleum. The method predicted more accurately on the specific gravity. Also, Yasar et al.
(2007) carried out the structural analysis of asphaltene fraction and combined the results obtained
with previous findings on elemental analysis. Consequently, the possible hypothetical molecular struc-
ture for saturated, aromatic, resin fraction was proposed (Yasar 2009). Furthermore, to characterize
Saudi crude oils, Siddiqui, Ali, and Shirokoff (2002) used the x-ray diffraction (XRD) technique,
while Bausal et al. 2007) used the same technique to characterize crude processed at two Indian
refineries. Diffraction techniques are primarily used in the structural and morphological analyses of
materials. Its versatility makes the technique an extremely powerful tool especially for the structural
analysis.
In this study, asphaltenes are derived by precipitation with n-pentane from bitumen, the heaviest
crude oil fractionates, from various localities in the South-western area of Nigeria. These are analyzed
by the XRD technique in order to elucidate the main molecular features that distinctly characterize them,
by means of various structural parameters.

2. Experiment

2.1. Sample collection and preparation

Five samples of oil sand outcrops were obtained from various locations in the South-western part of
Nigeria, namely: Ilubirin, Agbabu, Olowo-Irele, Loda, and Orisunbare. Solvent extraction on each of
these samples was carried out in a thimble using the Soxhlet extractor and Toluene as the extracting
solvent. A stream of nitrogen gas was employed to recover the extracting solvent and bitumen was con-
sequently obtained as the heaviest fraction of crude. This was subsequently treated with n-pentane using
the solute/solvent volume ratio 1:40 (Yasar et al. 2001). The mixture was stirred and left for 6 hr at 60°C
to form a precipitate of asphaltenes that were separated from maltene (n-pentane soluble) by filtration.
It was then washed with an equal volume of n-pentane. Boiling pentane was used to verify the absence
of maltene in the asphaltenes fraction, and the solvent was again recovered using a stream of nitrogen
gas. This was followed by drying the asphaltenes at 50°C in a vacuum oven until reaching a constant
weight. The treatment of the crude oil with n-pentane provided the asphaltene separation, while the
 PETROLEUM SCIENCE AND TECHNOLOGY 1669

maltene was removed from the filtrate by evaporation. The asphaltene samples derived from the oil sand
outcrops were subsequently denoted as AS1 , AS2 , AS3 , AS4, and AS5 .

2.2. Measurement of XRD spectra

A Philips analytical Rontgen Diffractometer Model PW3040/60X port PRO was used to record the XRD
spectra of samples. The measurement was taken from the goniometer scan axis in steps of 2θ , for a scan
time of 38.7 s, at a temperature of 25°C, using a CuKα radiation of wavelength λ = 1.5406 Å generated at
40 kV, 30 mA. Each specimen of 10 mm in length was well positioned on the scan axis of the goniometer
of radius 2.4 × 102 mm.
The operation of the device is based on the scattering of incident X-radiation off a collection of atoms.
At a given wavelength and angle of incidence of the source radiation, the scattering angle depends on
the atomic row spacing, d. For scattered rays from successive atomic rows that are in phase, diffraction
maxima are observable for short wavelength of the source radiation, hence the use of X-rays (Lagally
1985). The mirror reflection of the rays denoted the (00) band, the first and the second order diffrac-
tions denoted the (10) and (20) bands, respectively. Reconstructions of the diffracted waves may occur
in a periodic structure, producing other bands such as the (001) or (002). The positions and shapes
of diffracted beams also provide information about periodicity of structure and the degree of order of
structure, while the integrated intensity provides considerable value in quantitative analysis (Lagally and
Savage 1993).

Figure . XRD patterns of the asphaltene samples.

1670 J. O. AKINNIFESI ET AL.

Table . Features of the main peaks in the diffraction patterns of the five asphaltene samples.

Sample code Position (°θ ) Width half max (°θ ) d-spacing (Å) Relative intensity (%) Diffraction band

AS1 . . . . γ

. . . . 
. . . . 
. . . . 
AS2 . . . . 
. . . . 
. . . . 
AS3 . . . . 
. . . . 
. . . . 
AS4 . . . . γ
. . . . 
. . . . 
. . . . 
AS5 . . . . γ
. . . . 
. . . . 
. . . . 

AS1 = Ilubinrin; AS2 = Agbabu; AS3 = Olowo − Irele; AS4 = Loda, and AS5 = Orisunbare asphaltene samples.

3. Results and discussion

The XRD patterns of the various asphaltene samples are shown in Figure 1 (a)–(e), respectively.
These feature Bragg’s diffraction peaks at various positions and relative intensities. The summaries of
the features of the peaks associated with the respective XRD spectra corresponding to the samples are
presented in Tables 1.
From these results, several structural parameters of the asphaltenes can be deduced. The literature
reports that XRD patterns of asphaltenes have established the occurrence of four main characteristic
peaks: the gamma (γ ) band, (002) band, (10) band, and (11) band (Yen et al. 1961). The peak position
of the band provides information about the distance between the two aliphatic chains or saturated rings,
dr . Similarly, the distance between two aromatic sheets, dm , could be obtained from the peak position of
the (002) band. The size of the aromatic sheet, La, could be obtained from either the (10) or (11) band,
as well as the cluster diameter, Lc (Strausz et al. 1992). Consequently, the average number of aromatic
sheets Me and the average number of carbon atoms per aromatic structural unit CAU can be calculated
from the measured data. The respective equation for these structural parameters is listed as follows (Yen
et al. 1961):

◦ λ
dr (A ) = (1)
2 sin θr
◦ λ
dr (A ) = (2)
2 sin θ002
◦ 0.9λ 0.45
Le (A ) = = (3)
(ωcosθ002 ) B1/2
Lc
Me = (4)
dm
◦ 1.84λ 0.92
La ( A ) = = (5)
(ωcosθ10 ) B1/2
La
Ra = (6)
2.69
La + 1.23
CAU = (7)
0.65
 PETROLEUM SCIENCE AND TECHNOLOGY 1671

Table . Structural parameters of the respective asphaltene samples.

◦ ◦ ◦ ◦ ◦
Sample code dr (A ) dm ( A ) Lc (A ) Me La (A ) Ra (A ) CAU

AS . . . . . . .

AS – . . . . . .
AS – . . . . . .
AS . . . . . . .
AS . . . . . . .

AS1 = Ilubinrin; AS2 = Agbabu; AS3 = Olowo − Irele; AS4 = Loda, and AS5 = Orisunbare asphaltene samples.

where θr ,θ002 , and θ10 are diffraction angles of r, 002, and 10 bands, respectively. B1 is the width at half
/2
maximum of diffraction peak.
Using the data from Table 1, the structural parameters defined by Eqs. (1)–(7) were evaluated in
Table 2 for the respective samples.
From a comparative consideration of the structural parameters of the five asphaltene samples, it is
clear that the distance between the two aliphatic chains varies significantly in sample AS4, whereas the
distance between the aromatic sheets varies only slightly. It however varies significantly in sample AS5 .
The variations may have been due to the geological influences on the chains. However, Clemma et al.
(2002) in their study of the structure of asphaltenes of different aromaticity seamed similar in rings. The
probable hydrogenation of saturated rings during processing could also possibly result in shortening of
branch chains or the aggregation of aromatic units. Similarly, the size of aromatic sheet and the cluster
diameter vary accordingly in the samples. Moreover, the average number of aromatic sheets and the aver-
age number of carbon atoms per aromatic structural unit, CAU also vary accordingly. The latter parameter
however features a more significant variation across the samples. For samples AS3 and AS5 , however, the
values of La , Ra and CAU are identical. Decreasing values of carbon atoms per aromatic unit CAU suggest
smaller and fewer carbon aromatic sheets and aliphatic chains. Conversely, Soley et al. (2008) reported
that increasing aromaticity parameter is proportional to a large molecular size of hydrocarbon. In effect,
the variation in values of the structural parameters would determine the level of additive aromaticity
vis-a-vis its solubility to improve the liberation of the asphaltenes in better blends and invariably the
important operating parameters of the refining process.

4. Conclusions
The structure of bitumen-derived asphaltene from five different localities was studied by x-ray diffrac-
tometry. Analyses of the structural parameters revealed the degree of aromaticity in the various asphal-
◦
tene samples. The distance between aliphatic chains or saturated rings was highest (∼ 4.5 A) in one of
the five samples (AS4 ) that also had the lowest distance between aromatic sheets. This distance dm var-
ied only slightly (between 1.7 and 1.8 Å) in the four samples AS1 , AS2 , AS3 , and AS4 but varied quite
◦ ◦
significantly (∼ 3.7 A) in sample AS5 . The sample AS4 also presented the highest values of Lc (∼ 3.8 A),
◦ ◦ ◦ ◦
Me (∼ 4.1 A), La (∼ 3.4 A), Ra (∼ 1.3 A ), and Cau (∼ 5.3 A ). Significant variations in these values
occurred in the order AS2 > AS1 > AS3 = AS5 for the structural parameters, CAU , Ra and La , and in
order AS1 > AS3 > AS2 > AS5 for the parameters Lc and Me . The samples with larger sizes of aromatic
sheets dm , and higher numbers of carbon atoms per structural unit CAU would require solvents of high
aromaticity to increase solubility of aromatic components in them. This would lead to the liberation of
better blends of asphaltenes during refinement processes.

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