Article

pubs.acs.org/EF

Investigation on Asphaltene Structures during Venezuela Heavy Oil

Hydrocracking under Various Hydrogen Pressures
Dong Liu,*,† Zhongtao Li,† Yue Fu,‡ Yinghao Zhang,§ Peng Gao,† Caili Dai,*,† and Kaiyuan Zheng†
†
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266555, People’s Republic of China
‡
China National Offshore Oil Corporation, Beijing 100010, People’s Republic of China
§
Mechanical and Electrical Engineering Institute, Beijing Institute of Technology, Beijing 100010, People’s Republic of China

ABSTRACT: Venezuela heavy oil under various hydrogen pressures has been hydrocracked to investigate the variation of
asphaltene components during reaction. Asphaltenes have been isolated from the product and analyzed by X-ray diffraction
(XRD), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR). The experimental data
revealed that the interlamellar spacing and interchain spacing of the asphaltenes increased while the layer diameter decreased
with the hydrogen pressure increasing. At the same time, the amount of aromatic carbon and alkyl carbon of the asphaltenes
decreased gradually and the amount of naphthenic carbon increased. As the hydrogen pressure increased, the substitution ratio
and the condensation degree parameter (HAU/CA) of the aromatic system in the periphery increased gradually and the
replacement index and peri-position condensation index of asphaltenes decreased obviously.

1. INTRODUCTION Herein, asphaltenes of a suspended-bed hydrocracking

As one of the most complicated components in residue oil,
asphaltene is composed of various aromatic hydrocarbons with
a high content of heterocyclic compounds and a large molecular
weight.1,2 The micelle core structure of oil colloid plays an
important role in keeping the stability. Some increasing
attention has been focused on detecting the structure of the
asphaltenes during hydrogenation through size-exclusion
chromatography (SEC), small-angle neutron scattering
(SANS),3−5 1H nuclear magnetic resonance (NMR), elemental
analysis, and average relative molecule weight.6−8 Although
many significant conclusions have been obtained, the role of
hydrogen pressure during hydrocracking, structural changes of
components, and reaction mechanism during residue hydro-
genation have not been studied thoroughly and still need to be
further investigated.
With the progress of characterization methods, the structure
of asphaltenes has been well-studied. Modern analytical
instruments have been employed to readily detect routes that
can greatly improve the current research. The most useful
physical analytical instruments include NMR, Fourier transform
infrared (FTIR) spectroscopy, X-ray diffraction (XRD),
etc.,9−12 especially NMR, which has been considered as an
important way for heavy oil structural analysis. 1H NMR has
been widely used in the identification of aromatic protons and
saturated protons. It can also provide more details about the
hydrogen chemical environments for predicting distribution of
hydrogen types of compounds. 13C NMR can detect different
types of carbon directly. However, thousands of cyclic scans are
essential to obtain a reasonable spectrogram because of the very
low abundance of 13C in nature. X-ray is also applied to the
study of asphaltene structure very frequently. Yen and co-
workers13−15 obtained many parameters, such as layer diameter,
interlamellar spacing, interchain spacing, and number of layers,
from the X-ray signal in different angles.
product in different hydrogen pressures have been analyzed
by NMR, XRD, etc. The variations of structure composition
and parameters in asphaltenes have been described, and the
mechanism of asphaltenes in the process of heavy oil
hydrogenation in the presence of hydrogen pressure has also
been discussed.
2. EXPERIMENTAL SECTION
The Venezuelan heavy oil was used as raw materials. The Venezuelan
heavy oil hydrocracking was processed in a 0.5 L reactor for 1 h with
200 μg g−1 of oil-soluble molybdenum catalyst (calculated by the iron
naphthenate) under different initial hydrogen pressures (6.0−10.0
MPa) at 430 °C. The C7 asphaltenes was separated from the product
for further analysis.
Through traditional separation methods,16,17 four components
(saturate, aromatic, colloid, and asphaltenes) of residue oil have
been separated. Elemental analysis was performed using the Varil EL-3
elemental analyzer to define the contents of C, H, S, and N.
The asphaltenes was dissolved in toluene to measure the molecular
weight by a Knauwer molecular weight apparatus and calculated by the
method of vapor pressure osmometry (VPO). XRD was analyzed by
the D/MAX-IIIA X-ray diffractometer using a Cu target as the X-ray
source. XRD spectrograms of asphaltenes (products at different initial
hydrogen pressures) were calculated for monitoring the variations of
asphaltene lamellar structures.
A Bruker Avance DMX500-type superconducting NMR spectrom-
eter was used to determinate the 1H and 13C NMR spectra of
asphaltenes. CDCl3 was used as the solvent, and tetramethylsilane
(TMSi) was used as the internal standard. The resonance frequency
was 500 MHz.
Received: March 12, 2013
Revised: June 6, 2013
Published: June 20, 2013

© 2013 American Chemical Society 3692 dx.doi.org/10.1021/ef4003999 | Energy Fuels 2013, 27, 3692−3698
Energy & Fuels Article

3. RESULTS AND DISCUSSION radical increased with the increase of the hydrogen initial
3.1. Element and Component Analyses of the pressure, which hydrocracked the alkyl side chain of
Atmospheric Residue in the Hydrocracking Product asphaltenes. When the pressure increased higher, part of the
under Different Hydrogen Pressures. Venezuelan heavy oil aromatic system would be hydrogenated and cracked, resulting
was hydrocracked with various reaction pressures and 200 μg in the decrease of the asphaltene molecular weight.
g−1 of oil-soluble molybdenum catalyst at 430 °C. The 3.2. XRD Analysis of Asphaltenes in the Reaction
atmospheric residue has been analyzed, and the results are Product under Different Hydrogen Initial Pressures. The
shown in Table 1. asphaltenes of the cracking product at different hydrogen
pressures were analyzed by an X-ray diffractometer. Many
structural parameters, such as layer diameter (La), interlamellar
Table 1. Four-Component Analysis of the Atmospheric
spacing (dm), interchain spacing (dr), cell height (Lc), and
Residue
number of piles have been calculated. The XRD spectrogram of
initial hydrogen pressure (MPa) 6 8 10 AR asphaltenes of the product at the initial hydrogen pressure
saturate (%) 34.83 40.02 42.56 of 10 MPa is shown in Figure 1.
aromatic (%) 39.84 39.08 38.28
resin (%) 11.32 12.90 13.06
asphaltene (%) 12.43 9.958 6.103

As shown in Table 1, the content of the saturate component

increases with the hydrogen pressure increasing, revealing that
the hydrocracking reaction and side-chain cracking reaction
took place. The aromatic content slightly changed because of
the dynamic equilibrium between composition and decom-
position at high hydrogen pressure and temperature. Because
two reactions cooperated simultaneously with each other, the
aromatic content was kept at the same level during hydro-
cracking. The asphaltene content decreased dramatically
because the high initial hydrogen pressure constrained the
condensation of the aromatic with resin. More hydrogen
radicals were formed under high initial hydrogen pressure, and
these radicals neutralized the aromatic radicals that generated
during cracking. Therefore, the resin content slightly increased, Figure 1. XRD spectrum of asphaltenes in the product at 10 MPa.
and the asphaltene content decreased. Furthermore, a large
number of hydrogen radicals also constrained the cross-linking
of macromolecular radicals to prevent the generation of coke. From the XRD spectrogram, Bragg angle 2θ is 42.48°, λ =
Venezuelan heavy oil was hydrocracked under different 1.5406 nm, and the other structural parameters are calculated as
hydrogen pressures at 430 °C. The results of elemental analysis follows:
of asphaltenes in the product are tabulated in Table 2.
interlamellar spacing
Table 2. Elemental Composition of Asphaltenes in the dm = λ/2 sin θ
Reaction Products under Different Hydrogen Pressures
interchain spacing
initial hydrogen C H S N molecular
pressure (MPa) (wt %) (wt %) (wt %) (wt %) weight dr = 5λ /8 sin θ
6 85.11 8.36 3.48 1.91 3438.9 layer diameter
8 84.09 9.73 2.94 1.84 3356.2
10 83.41 9.88 2.54 1.59 3201.6
La = 1.84λ /ω cos θ = 0.92/B1/2
cell height
As seen in Table 2, the content of carbon in the asphaltenes Lc = 0.9λ /ω cos θ = 0.45B
gradually decreased with an increasing of initial hydrogen
pressure, while the content of hydrogen increased. Under a low layer number
initial hydrogen pressure, the macromolecule radicals were
Me = (Lc/dm) + 1
dramatically correlated with each other, which led to the
increasing content of carbon in asphaltenes. Thus, secondary average ring number at any orientation
asphaltenes generated easily and tended to coke. A higher initial
hydrogen pressure played a positive role on hydrogenolysis
Ra = La/2.667
reaction, such as hydrodesulfurization and hydrodenitrogenera- where θ is the diffracion angle, λ is the X-ray optical
tion. As a result, the C, S, and N contents in asphaltenes wavelength, ω is the peak width, B1/2 is the full width at half
decreased under higher hydrogen pressure. maximum, and 2.667 Å is the width of a single aromatic
At the same time, it can be seen that the asphaltene molecule nucleus.
weight of atmospheric residue (AR) in product decreased The crystal parameters of asphaltenes in the product under
obviously with the increase of the initial hydrogen pressure. different hydrogen pressures can be calculated by a similar
The reason would be that the concentration of the hydrogen method. The results are shown in Table 3.
3693 dx.doi.org/10.1021/ef4003999 | Energy Fuels 2013, 27, 3692−3698
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Table 3. Crystalline Parameters of Asphaltenes at Different dominated, which gave rise to the increase of asphaltene
Hydrogen Pressures sheet diameter. When the initial hydrogen pressure increased,
the macromolecule radicals of asphaltenes were terminated by a
initial hydrogen pressure (MPa) 6 8 10
large number of hydrogen radicals. Thus, condensation
interlamellar spacing (Å) 5.618 6.116 6.543 between radicals slowed, and the hydrogenolysis reaction
interchain spacing (Å) 7.022 7.645 8.179 could occur in the cata-condensation carbon and peripheral
layer diameter (Å) 13.333 12.432 11.5 carbon of the aromatic ring system, resulting in a decrease of
cell height (Å) 6.522 6.081 5.625 the asphaltene layer diameter.
number of piles 3.373 3.033 2.758 The layer number and the number of rings of asphaltenes
average ring number at any orientation 4.999 4.662 4.312 decreased with the increase of the initial hydrogen pressure. At
a lower hydrogen pressure, the condensation reaction of
The variation tendency of interlamellar spacing, interchain aromatic radicals took place dramatically, which increased the
spacing, and chain diameter of asphaltenes of the hydrocracking condensation rate among different layers of asphaltenes. When
product at different hydrogen pressures was listed in Table 3. the hydrogen pressure increased, this condensation reaction
The experimental data revealed that interlamellar and would be weakened; therefore, the layer number and number of
interchain space of the product asphaltenes increased and the rings decreased.
chain diameter decreased with the increase of the hydrogen 3.3. 1H NMR Analysis of Asphaltenes under Different
pressure, demonstrating that a higher hydrogen pressure Hydrogen Initial Pressures. According to the 1H NMR data
weakened the interaction between asphaltene layers and relaxed of asphaltenes from the product under different hydrogen
the layer-by-layer structure. The aliphatic chains could be pressures, the average structural parameters of asphaltenes were
cracked in the hydrocracking. Thus, the interlayer space and calculated in terms of the Browen−Landner method.18,19 The
curvature of the layers became smaller, which led to an increase asphaltene 1H NMR spectrum of the hydrocracked product
of the distance between the aliphatic chains. When the under a 10 MPa hydrogen atmosphere is shown in Figure 2.
hydrogen pressure was lower, the condensation reaction The intensities of various protons were calculated by peak
between macromolecule radicals of asphaltenes became integration. According to the Browen−Landner method, the

Figure 2. 1H NMR of asphaltenes from the product under 10 MPa.

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types of carbon atoms of asphaltenes in the product under during which radical generation and connection reacted
different hydrogen pressures are shown in Table 4. simultaneously. Therefore, the higher initial hydrogen pressure
would prevent the linking of the macromolecule radical from
Table 4. Average Structural Parameters of Asphaltenes from forming a polyaromatic system. Thus, the aromatic carbon rate,
the Product under Different Hydrogen Pressures total ring number, aromatic carbon number, and aromatic ring
number decreased significantly. Moreover, a high initial
symbol name 6 MPa 8 MPa 10 MPa hydrogen pressure could accelerate the hydrogenolysis reaction,
CT total carbon 243.9 235.2 222.5 and some periphery aromatic rings hydrogenated and saturated
fA aromatic rate 0.5624 0.5089 0.4845 into a naphthenic ring, which led to the increase of the
CA aromatic carbon 137.2 119.7 74.44 naphthenic ring number. The decrease of the total carbon
σ replacement rate of periphery 0.3328 0.3574 0.3822 number of asphaltenes may be ascribed to the main reaction of
hydrogen in the aromatic ring
system the hydrogenolysis reaction under a higher initial hydrogen
HAU/ condensation degree parameter of 0.3903 0.5257 0.6417 pressure, which could lead to weakening of the interlayer
CA the aromatic ring system interactions of the asphaltenes and loosing of asphaltene layers
RT total ring number 53.15 51.38 38.79 from each other. Therefore, some chains of the aromatic ring
RA aromatic ring number 44.39 38.56 23.48 system would be broken, and even some smaller laminas in the
RN naphthenic ring number 8.756 12.82 15.31 hydrogenation process might be separated, giving rise to a
CS saturated carbon number 106.8 114.72 115.5 decrease of the total carbon number of asphaltenes.
CN cycloalkyl carbon number 26.27 38.45 45.93 From Table 4, the substituted rate of the aromatic protons
Cp paraffin carbon number 80.51 77.05 68.78 gradually increased with the increase of the reactive hydrogen
fN naphthenic carbon rate 0.1077 0.1635 0.2064 pressure, which was caused by the hydrogenation of periphery
fP paraffin carbon rate 0.3301 0.3276 0.3091 aromatic rings of asphaltenes. The higher initial hydrogen
pressure played a positive role on the hydrogenation of the
As shown in Table 4, with the initial hydrogen pressure aromatic ring, and some kinetic studies indicated that the ring-
increasing, the variation of average structural parameters of opening reaction of the naphthenic ring could be inhibited
asphaltenes in the product abode by the following rules: the under the high initial hydrogen pressure.20,21 When the rate of
total carbon number, total ring number, aromatic carbon hydrogenation was higher than that of naphthenic ring opening,
number, and aromatic ring number decreased with the great the substitution rate of aromatic protons would increase and
decrease of the aromatic carbon rate, while the naphthenic ring the number of naphthenic ring also increased. This was also the
number increased. For the heavy oil suspension-bed hydro- reason for the increase of the naphthenic ring and number of
cracking, most of the thermal reactions were radical reactions, naphthenic carbons. Under different hydrogen pressures, the

Figure 3. 13C NMR of asphaltenes from the product at 10 MPa.

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condensation degree parameter HAU/CA of products increased saturated carbon in asphaltenes. While the condensation
with the increase of the hydrogen pressure, meaning a smaller reaction led to more aromatic compounds, the content of
condensation degree of the aromatic ring. aromatic carbon and endocyclic carbon in the product
3.4. 13C NMR Analysis of Asphaltenes in Hydro- increased. However, the concentration of hydrogen radicals
cracked Venezuelan Heavy Oil. The ratio of different types increased with the initial hydrogen pressure increasing,
of carbon atoms in asphaltenes was calculated from the 13C generating more cycloalkane rings by the hydrogenation
NMR spectrum, and the results are shown in Figure 3 and reaction of the aromatic ring. The restraint of cracking resulted
Table 5. in the decrease of side chains breaking and the increase of
saturated carbon. The higher initial hydrogen pressure
Table 5. Distribution of the Different Types of Carbon terminated radical chain transfer by the linking of hydrogen
Atoms in Asphaltenes radicals and macromolecule radicals, causing the decrease of
aromatic carbon and inner carbon of the aromatic ring system.
6 MPa 8 MPa 10 MPa
type (%) (%) (%) As shown in Table 5, the number of peripheral aliphatic
carbonyl carbon 0.4072 0.2818 0.0621 substituted carbons was gradually reduced with the increase of
peripheral carbon of the 14.49 12.19 10.79 hydrogen pressure. This may be assigned to the decrease of the
aromatic system generation of the hydrogen radical with the reduction of the
substituted by an initial hydrogen pressure. Therefore, aromatic ring radicals and
aliphatic chain
aromatic peripheral carbon of the 24.26 25.32 26.51
aliphatic chain radicals were ready to cross-link with each other.
carbon aromatic system However, when the hydrogen pressure increased, the
unsubstituted by an concentration of hydrogen radicals in the reaction system
aliphatic chain
became higher and the hydrogenolysis reaction was strength-
inner carbon of the 16.87 13.50 11.90
aromatic ring system ened; therefore, the peripheral aliphatic substituted carbons in
aromatic carbon 55.63 51.02 49.21 the aromatic ring decreased. At the same time, secondary
methyl 7.965 10.10 13.25 asphaltenes was also generated because of the condensation
substituted methylene 32.63 35.35 37.34 reaction of the aromatic ring radical, resulting in the increase of
carbon tertiary carbon 3.392 3.255 0.1449 the unsubstituted peripheral carbon of the aromatic ring system
saturated carbon 43.96 48.70 50.73 in asphaltenes.
The content of carbonyl carbon obviously reduced with the
From Table 5, it can be found that the aromatic carbon and increase of the initial hydrogen pressure. At the low initial
endocyclic carbon in asphaltenes gradually reduced with the hydrogen pressure, the hydroxyl was generated by hydro-
increase of hydrogen pressure, while the content of saturated genation of carbonyl, while at the high initial hydrogen
carbon significantly increased. The reason would be that the pressure, the hydroxyl would react further. The infrared spectra
main reaction of Venezuelan heavy oil in the slurry-bed of asphaltenes (Figure 4), which were generated under a
hydrocracking contains a thermal reaction, a cracking reaction, pressure of 5 MPa (red line) and 10 MPa (blue line), revealed
and a radical condensation reaction. The side chains of the that there was a 3300 cm−1 absorption peak in the 5 MPa
aliphatic were broken by cracking under low hydrogen pressure asphaltenes, while this absorption peak was weakened for the
and high temperature, leading to the obvious decrease of 10 MPa asphaltene IR spectra, indicating that the content of

Figure 4. Infrared spectra of asphaltenes of the product at 5 and 10 MPa.

3696 dx.doi.org/10.1021/ef4003999 | Energy Fuels 2013, 27, 3692−3698

Energy & Fuels
carbonyl carbons in produced asphaltenes gradually decreased
with the improvement of the hydrogen pressure.
The saturated carbon of asphaltenes was substantially free of
quaternary carbon and also with a relatively small amount of
tertiary carbon. As shown in Table 5, the content of the methyl
and methylene increased and the tertiary carbon content
significantly decreased with the increase of the initial hydrogen
pressure. It may be due to the more active and reactive β-
hydrogen on the side chain of the aromatic ring under high
hydrogen pressure. After cracking, the methyl still connected
with the aromatic ring, which was attributed to the increase of
the methyl with the increase of the pressure. The increasing
content of methylene was primarily ascribed to the generation
of the cycloalkyl ring during the aromatic ring hydrogenation
under a high initial hydrogen pressure.
The 13C NMR was used to characterize the structure of
asphaltenes by Gauthie and co-workers,22 and the peri-
condensation index and replacement index were employed to
characterize the changes of the structure of asphaltenes. The
substituted index and the condensation index of raw material
and products under different hydrogen partial pressures were
calculated.
As shown in Table 6, the substituted index and the peri-
condensation index decreased dramatically with the increase of
Table 6. Substitution Index and Condensation Index of
Asphaltenes in the Reaction Product at Different Hydrogen
Pressures
type 6 MPa 8 MPa 10 MPa
replacement index 0.3738 0.3249 0.2892
peri-condensation index 3.312 2.686 2.405
the hydrogen pressure. This may be ascribed to saturation of
the aromatic rings in asphaltenes by hydrogenation at a high
initial hydrogen pressure during the generation of the
naphthenic ring. At a high temperature and high hydrogen
pressure, the following ring opening and side chain cleavage of
the cycloalkyl ring reactions could occur; therefore, the
substituted index showed a reducing trend with the increase
of the hydrogen pressure. While the aromatic rings at the edge
of the conjugated system were saturated by hydrogenation and
finally broken, the original internal peri-condensed melting
carbon would become the peripheral carbon and the peri-
condensation index declined obviously.
4. CONCLUSION
Venezuelan heavy oil has been hydrocracked under various
initial hydrogen pressures to investigate the influencing factors
and mechanism during the reaction. Experimental data revealed
that the interlamellar space and interchain space of asphaltenes
increased with the increase of the pressure, while the diameter
of each layer decreased. While the aromatic carbon and alkyl
carbon in asphaltenes decreased gradually, the naphthenic
carbon increased. The aromatic carbon and aliphatic substituted
aromatic carbon decreased obviously. Finally, the replacement
index and peri-position condensation index of asphaltenes
decreased with the increase of the initial hydrogen pressure.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: liudong@upc.edu.cn (D.L.); daicl@upc.edu.cn (C.D.).
3697
Article
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledge financial support from the
Natural Science Foundation of China (21176259) and the
award from the Foundation for Excellent Young and Middle-
Aged Scientist of Shandong Province, China (BS2010NJ024).
■
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