Article

pubs.acs.org/EF

Size Distributions of Sulfur, Vanadium, and Nickel Compounds in

Crude Oils, Residues, and Their Saturate, Aromatic, Resin, and
Asphaltene Fractions Determined by Gel Permeation
Chromatography Inductively Coupled Plasma High-Resolution Mass
Spectrometry
German Gascon,†,‡,§ Vicmary Vargas,‡,§,∥ Llinaber Feo,† Olga Castellano,† Jimy Castillo,∥ Pierre Giusti,⊥
Socrates Acavedo,∥ Charles-Philippe Lienemann,# and Brice Bouyssiere*,‡,§
†
PDVSA Intevep, Apartado 76343, Caracas 1070-A, Venezuela
‡
Institut des Sciences Analytiques et de Physico-Chimie pour l’Environnement et les Materiaux, UMR 5254, Centre National de la
Recherche Scientifique (CNRS)/Université de Pau et des Pays de l’Adour, 64000 Pau, France
§
Joint Laboratory C2MC: Complex Matrices Molecular Characterization, Total Research & Technology, Gonfreville, BP 27, F-76700
Harfleur, France
∥
Escuela de Química, Facultad de Ciencias, Universidad Central de Venezuela (UCV), Caracas 1053, Venezuela
⊥
TOTAL Raffinage Chimie (TRTG), BP 27, 76700 Harfleur, France
#
IFP Energies nouvelles-Lyon, Rond-point de l’échangeur de Solaize, BP 3, 69360 Solaize, France

ABSTRACT: The size distributions of sulfur (S), vanadium (V), and nickel (Ni) compounds in four crude oils, two residues,
and their saturate, aromatic, resin, and asphaltene (SARA) fractions were determined using gel permeation chromatography
(GPC) coupled to inductively coupled plasma high-resolution mass spectrometry (ICP HR MS). The results show trimodal
distributions of V, Ni, and S compounds in the crude oils and residues. V and Ni compounds are present in both resins and
asphaltenes. Trimodal distributions are clearly apparent in the resins but not apparent in the asphaltenes. In the latter, the
predominant compounds have a high molecular weight (HMW), even when the solution of asphaltenes is diluted by 40000-fold.
In the resins, compounds with a medium molecular weight (MMW) were expected; however, HMW compounds were observed,
indicating that nanoaggregates or large molecules exist in both the asphaltenes and resins. Low-molecular-weight (LMW)
compounds are predominantly present in the resins and do not represent more than 22% of V and Ni present in crude oil. These
compounds appear to have molecular weights similar to simple metalloporphyrins.

■ INTRODUCTION
Crude oil is a very complex mixture primarily composed of
carbon, hydrogen, sulfur, nitrogen, and trace metals [nickel
(Ni) and vanadium (V)].1 The oil quality is defined by the
types of hydrocarbons and potential contaminant species that
are present. Among the metals naturally present in crude oil, V
and Ni are the most abundant.1 Because of their high boiling
point, minimal V and Ni are contained in the distillates (<375
°C); the majority are present in the vacuum residue.2
Additionally, the low solubility of several V and Ni compounds
in most (if not all) solvents, specifically metalloporphyrins
(MPs),3−5 facilitates a partitioning between the asphaltenes and
maltenes. The specific relationship between these two fractions
depends upon the solvent used to precipitate the asphaltenes.6,7
The metallocompounds (MCs) soluble in maltenes are
principally found in the resins.8,9 With regard to the nature
of V and Ni compounds present in crude oil, several MPs have
been identified,10−13 although the amount of known species
represents a minor part of the total V and Ni present in crude
oil. Because not all of the V and Ni present in the asphaltenes
(and crude oil) can be accounted for by the MPs (less than
50%, as estimated by elemental analysis), the existence of non-
porphyrinic compounds has been proposed.14−17 These
compounds include other ring systems, such as chlorophylls,
chlorins, corrins (reduced porphyrins), highly substituted
aromatic porphyrins, and porphyrins with ultraviolet−visible
(UV−vis) properties (unlike porphyrins that exhibit the Soret
band).14 However, much controversy exists regarding non-
porphyrinic compounds18,19 and several hypotheses suggesting
that all V and Ni present in crude oil are MPs20 and that some
may be trapped in either asphaltene aggregates in solution,21−25
in a supramolecular assembly of molecules,26 or in large
molecules.27,28 Large compounds containing V and Ni have
been investigated using size-exclusion chromatography (SEC)
or gel permeation chromatography (GPC) coupled with
inductively coupled plasma optical emission spectroscopy
(ICP OES)17,29 or inductively coupled plasma mass spectrom-
etry (ICP MS),2 and a bimodal distribution of V has been
found with maxima at approximate molecular weights (MWs)
of 800 and 9000 [polystyrene (PS) equivalent].17 In contrast,
Received: February 21, 2017
Revised: May 31, 2017
Published: June 21, 2017

© 2017 American Chemical Society 7783 DOI: 10.1021/acs.energyfuels.7b00527

Energy Fuels 2017, 31, 7783−7788
Energy & Fuels Article

Table 1. Percentage Distributions of V, Ni, and S in Crude Oils, Residues, and Their SARA Fractionsa
total saturates aromatics resins C7 asphaltenes mass balance
sample info (mg/kg, %) [ppm (mg/kg, %)] [ppm (mg/kg, %)] [ppm (mg/kg, %)] [ppm (mg/kg, %)] (%)
CO1 % SARA 19 23 39 17
V 416.7 1.4 (0.1) 2.5 (0.1) 553 (49.2) 1306 (50.6) 105.2
Ni 102.2 0.6 (0.1) 2.9 (0.6) 141 (49.9) 319 (49.4) 107.6
S 34500 2772 (1.6) 40018 (28.8) 42374 (51.6) 33866 (18.0) 109.7
CO2 % SARA 22 30 34 12
V 472.8 2.3 (0.1) 0.3 (0.0) 802 (53.5) 1967 (46.3) 107.7
Ni 100.8 0.6 (0.1) 2.5 (0.7) 185 (55.8) 408 (43.4) 111.8
S 35000 2603 (1.7) 42093 (38.2) 44967 (46.2) 38351 (13.9) 94.5
CO3 % SARA 31 34 29 7
V 432.4 2.2 (0.1) 1.7 (0.1) 980 (61.1) 2561 (38.6) 107.5
Ni 57.4 0.6 (0.3) 1.3 (0.7) 127 (60.1) 341 (38.9) 106.9
S 26260 2595 (3.2) 33808 (45.2) 36478 (41.6) 36156 (10.0) 111.1
CO4 % SARA 35 25 25 6
V 459.5 0.6 (0.0) 23.1 (1.2) 1019 (51.6) 3884 (47.2) 107.5
Ni 51.3 0.2 (0.2) 4.8 (2.2) 112 (52.2) 404 (45.4) 104.2
S 23250 2821 (4.3) 44962 (48.8) 32254 (35.0) 45991 (12.0) 99.1
VR % SARA 16 33 36 15
V 141.4 0.8 (0.1) 2.1 (0.5) 167 (41.8) 554 (57.7) 104.4
Ni 44.6 0.5 (0.2) 1.5 (1.1) 51.1 (41.0) 172.6 (57.7) 100.6
S 49470 1726 (0.7) 46735 (38.0) 43381 (38.5) 61672 (22.8) 103.1
AR % SARA 17 35 34 14
V 576.2 0.5 (0.0) 5.2 (0.3) 762 (41.5) 2596 (58.2) 108.4
Ni 125.2 0.2 (0.0) 4.5 (0.1) 183 (44.8) 534 (54.0) 110.6
S 41300 3851 (1.8) 48178 (45.8) 35819 (33.0) 51101 (19.4) 103.1
a
The parentheses show the repartition (in percent) of the element between the SARA fraction with regard to the total in the crude oil.

trimodal distributions, divided into high-, medium-, and low-
molecular-weight (HMW, MMW, and LMW) components,
have been reported for V and Ni in various crude oils and
residues.2 With regard to the size distributions of V and Ni in
saturate, aromatic, resin, and asphaltene (SARA) fractions, Park
et al.30 recently measured these distributions in asphaltenes and
resins to different atmospheric residues (ARs) using SEC−ICP
MS [the size distribution for sulfur (S) was not reported]. The
strongly believe that improved demetallization strategies can be
realized if the size distributions of V, Ni, and S compounds are
known in the heavier fractions of crude oils and residues. This
knowledge would allow for the oil industry to select and design
better catalysts for the conversion of heavier fractions. For
example, the use of more active, smaller pored catalysts to
process deasphalted oil (DAO) has been recommended.35 The
importance of removing V and Ni compounds has previously
been mentioned.1,36,37

distributions are dramatically different from those reported by
Reynolds and Biggs29 and other works studying size
distributions only in asphaltenes.21 We believe this difference
results from the nature of the crude oil and residues studied.
Using SEC for this type of characterization has been
questioned,18 and several limitations should be noted. These
include the dependence of MW on the solvent used, the
interactions that form between PS particles and asphaltenes, the
use of PS to calibrate SEC columns,31 and individual
parameters relayed to columns and flow.32 However, the
technique continues to be important for discriminating the size
distributions of compounds that occur naturally in crude oil,33
including V, Ni, and S, which cannot be measured using other
techniques, such as matrix-assisted laser desorption/ionization
mass spectrometry (MALDI−MS)19 or Fourier transform ion
cyclotron resonance mass spectrometry (FT-ICR MS).10 The
results obtained from SEC provide insight into the interactions
of important components in V, Ni, and S present in heavier
fractions of crude oil, such as resins and asphaltenes. The best
solvent for ascertaining the size distributions of asphaltenes
using SEC has been reported to be tetrahydrofuran (THF).34
On the basis of the preceding discussion, we proposed to
determine the size distributions of different crude oils and their
SARA fractions using SEC−ICP high-resolution (HR) MS and
complete the work presented by Desprez et al.2 because we
■
MATERIALS AND METHODS
Instrumentation. The detailed conditions for ICP MS detection
have been previously reported,2 and a summarized description is given
below. An ICP HR MS (Element XR, Thermo Scientific) instrument
operated at a resolution of 4000 was used to access spectrally
interfered isotopes of 60 Ni, 32 S, and 51 V. The mass spectrometer
was equipped with a quartz injector (1.0 mm inner diameter), a Pt
sampler cone (1.1 mm orifice diameter), a Pt skimmer cone (0.8 mm
orifice diameter), an interface based on microflow total consumption,
and a nebulizer (DS5, Teledyne CETAC) mounted on a glass spray
chamber without a drain kept at 60 °C with a water−glycol mixture
using a temperature-controlled bath circulator (NESLAB RTE-111,
Thermo Fisher Scientific) to minimize signal suppression and increase
the sensitivity by 3−4-fold compared to existing setups, as described
elsewhere.38 An oxygen flow of 0.08 mL/min was continuously added
to the nebulizer Ar gas flow to avoid the deposition of carbon on the
cones. High-performance liquid chromatography (HPLC, UltiMate
3000, Dionex) was used for the coupling.
Reagents, Samples, and Materials. n-Heptane was used to
precipitate the asphaltenes, and toluene, methanol, and THF (all
HPLC-grade from Sharlau) were used for the fractionation of the
maltenes. The chromatography column (l = 50 cm, and inner diameter
= 2.5 cm) was filled with alumina CG-20 (Sigma-Aldrich). For the
GPC experiments, THF was used for the sample dilutions and as the
mobile phase. Samples of four Venezuelan crude oils, which were
identified as CO1, CO2, CO3, and CO4 on the basis of their high V

7784 DOI: 10.1021/acs.energyfuels.7b00527

Energy Fuels 2017, 31, 7783−7788
Energy & Fuels Article

and Ni contents, two residues of different crude oils, and their SARA
fractions were analyzed. The samples were prepared at different
concentrations in THF for the GPC analyses. Resins, crude oils, and
residues were diluted 100-fold, whereas saturates and aromatics were
diluted 50-fold because of their reported low concentrations of V and
Ni.8,9 The asphaltenes were diluted 200-fold. The separations were
carried out using three styrene−divinylbenzene gel permeation
columns connected in series (inner diameter = 7.8 mm, and l = 300
mm) in the following order: HR4, HR2, and HR0.5 (all Styragel). A
guard column (inner diameter = 4.6 mm, and l = 30 mm) was used to
protect the columns and increase their lifetime. To evaluate the
reproducibility of the system, the vanadium reference standards
2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine vanadium(IV) oxide
(V600) and vanadyl 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine
(V948) were evaluated.
Oil Fractionation. The fractionation of crude oil included two
separation steps: (1) precipitation of the asphaltenes with n-heptane
and (2) fractionation of the maltenes by chromatography. To avoid Figure 1. Size distributions of V in CO1 as well as its asphaltenes and
variations in the mass balance caused by evaporation losses of light resins.
hydrocarbons, all oil samples (2 g) were heated overnight at 80 °C
before further use. The samples (after evaporation) were mixed with
80 mL of n-heptane and maintained at 70 °C for 1 h. The precipitated
asphaltenes were separated by filtration with 2.5 μm Whatman filter
paper. The precipitate was washed with hot heptane until the heptane
wash was colorless. The washed precipitate was combined with the
maltenes. The asphaltenes were dried at 70 °C. The maltene fraction
was rota-evaporated, dissolved (1.5 g) in heptane, and placed on top of
the column filled with calcined CG-20 alumina for separation into the
SARA fractions by pumping an eluotropic series of elution solvents at
a flow rate of 3.0 mL/min. The saturates were eluted with 300 mL of
heptane and then toluene until a fluorescent orange band reached the
bottom of the column. The aromatics were eluted with a 1:1 toluene/
methanol mixture until a dark band reached the bottom of the column.
The resins were eluted with THF. The eluted fractions were recovered
by removing the solvent prior to the final weighing.
GPC and ICP MS Detection. A 20 μL sample was injected and
isocratically eluted at a THF flow rate of 1 mL/min for 120 min. A Figure 2. Size distributions of Ni in CO1 as well as its asphaltenes and
post-column splitter was used to divide the flow between a low-flow resins.
outlet of 50 μL/min to feed ICP MS and a high-flow outlet of 950 μL/
min that was discarded. The sensitivity of the columns during the
separation was evaluated using a mixture of PS standards and a
refractive index detector. A Microsoft Excel program was used to
deconvolute the chromatograms by summing the Gaussian curves.

■ RESULTS AND DISCUSSION

Percentage Distributions of V, Ni, and S. The total
concentration in each crude oil and residue evaluated is
presented in Table 1, along with the mass balances and the
partitions of the three studied elements in the SARA fractions.
Note that approximately 40−60% of the V and Ni content
present in the crude oil or residue is concentrated in the
asphaltene fraction, whereas the remaining content (between
60 and 40%) is in the resins. The differences between the
samples are attributed to the nature of the crude oil. The
percentage of sulfur was mainly distributed between the resin
and aromatic fractions, indicating that S compounds with
medium polarity predominate in the crude oil. In contrast, the Figure 3. Size distribution of S in CO1 and its SARA fractions.
V and Ni compounds that are present in the fractions have a
higher polarity (resins and asphaltenes).8,9 In all samples
evaluated, the concentration of V was greater than that of Ni.
Size Distributions of V, Ni, and S Compounds. monomodal distribution occurred (Ni in aspahltenes and S in
Trimodal size distributions were observed for the V compounds saturates, aromatics, and asphaltenes), whereas others showed
in CO1 as well as its resins and asphaltenes. These distributions bimodal (S in resins) or trimodal (Ni in resins) distributions.
are shown in Figure 1 and are labeled as HMW, MMW, and The analysis time was 120 min; however, the equivalent in
LMW compounds, consistent with the nomenclature previously seconds of elution time (between 18 and 35 min) is displayed.
used.2 For Ni (Figure 2) and S (Figure 3), a less pronounced The integration boundaries were chosen according to the
trimodal distribution was observed; in some fractions, a simple trimodal distribution of the V compounds.
7785 DOI: 10.1021/acs.energyfuels.7b00527
Energy Fuels 2017, 31, 7783−7788
Energy & Fuels
Molecular Weight of the Different Zones. Because of a
lack of standards for V with a HMW, estimations for the HMW
compounds were not attained. In contrast, through a
comparison of the elution with the reference standards V600
and V948, we estimate that the previously reported free
MPs10−13 are in the LMW zone and partially in the MMW
zone (Figure 4).
Figure 4. Relative comparison of V standards to V in CO1 as well as
its resins and asphaltenes.
Percentage Distributions of HMW, MMW, and LMW
Compounds of V and S. The exact size distributions of V in
the different crude oils and residues evaluated as well as in their
resins and asphaltenes are shown in Figure 5. As shown, the
LMW V compounds represent between 13 and 22% of the total
V present in the crude oils and residues, with the remainder
similarly distributed between MMW (30−40%) and HMW
(40−50%) compounds. It is important to note that the resin
fraction was clearly dominated by MMW compounds, whereas
the asphaltenes were dominated by HMW compounds. Similar
results were obtained for Ni; therefore, its distribution is not
presented.
For the S compounds, the distributions in the crude oils and
residues evaluated and in the resins, asphaltenes, and aromatics
are shown in Figure 6 (the distribution in saturates has been
omitted). In the crude oils, residues, resins, and aromatics,
MMW compounds predominated, whereas HMW compounds
Figure 5. Percentages of HMW, MMW, and LMW compounds of V in (a) crude oils and residues, (b) asphaltenes, and (c) resins.
7786
Article
predominated in the asphaltenes. Because of the high sensitivity
of the method used, V and S compounds with HMW, MMW,
and LMW were identified in all fractions.
Effect of the Dilution of Asphaltene on the Profile
Obtained Using GPC−ICP HR MS. According to the
literature, the HMW components of asphaltenes are a
consequence of aggregation.34,39 However, according to
different models, this aggregation occurs naturally in crude
oil.21,22,24−26 In fact, 90 wt % of the asphaltenes are self-
associated nanoaggregates with an average diameter ranging
from 5 to 9 nm and a maximum size of up to 20 nm.40
Additionally, according to Dechaine and Gray,41 (1) the
interchange of material between the aggregates and free
solution was extremely low, (2) an increase in the temperature
enhanced the asphaltene mobility but did not reduce the size of
the asphaltene structures below 5 nm, (3) a decrease in the
concentration to 0.1 g/L (100 ppm) did not result in a decrease
in size, and (4) the origin of the asphaltenes (Athabasca,
Safaniya, and Venezuela) did not substantially influence the
observed behavior.
To evaluate the effect of dilution on the asphaltene
distribution from our results and detection system, we
determined the size distribution of the asphaltene fraction
obtained from CO4 because of its high concentration of V
(3700 ppm). As shown in Figure 7, the ratio between HMW V
compounds and V total is relatively stable, even at
concentrations higher than 100 mg/kg of asphaltenes in THF
(Figure 7). At concentrations under 100 mg/kg, HMW
compounds of V (Figure 8) and S (Figure 9) were observed,
even after dilution of the asphaltene solution by 40000-fold. On
the basis of these results, we speculate that these compounds
may occur naturally in crude oil and may be similar to the
nanoaggregates reported by Dickie and Yen22 and Mullins et
al.25 or to a supramolecular assembly of molecules.26,27
■
CONCLUSION
The V and Ni compounds present in the crude oils and
residues evaluated are partitioned similarly between the resins
(40−60%) and asphaltenes (40−60%). In contrast, the S
compounds are mainly concentrated in the aromatics and resins
(75−90%), and only 10−25% are present in asphaltenes. With
regard to size distribution, HMW, MMW, and LMW
compounds of V, Ni, and S were observed in the crude oils
and residues evaluated.
DOI: 10.1021/acs.energyfuels.7b00527
Energy Fuels 2017, 31, 7783−7788
Energy & Fuels Article

Figure 6. Percentages of HMW, MMW, and LMW compounds of S in (a) crude oils and residues, (b) asphaltenes, (c) resins, and (d) aromatics.

Figure 7. Ratio of V HMW in asphaltenes of CO4 and concentrations

in THF at different dilutions determined by SEC−ICP HR MS.

Figure 9. Size distributions of HMW S compounds in asphaltenes

from CO4 at different dilutions in THF.

equally partitioned between MMW (30−40%) and HMW

(40−50%) compounds. We speculate that these compounds
are similar to nanoaggregates or trapped or larger molecules.
MMW compounds were predominant in resins and HMW
compounds in asphaltenes. HMW compounds were even
observed in an asphaltene solution that was diluted by 40000-
fold (25 mg/kg).

■ AUTHOR INFORMATION
Corresponding Author
*Telephone: +33-559-407-752. Fax: +33-559-407-674. E-mail:
brice.bouyssiere@univ-pau.fr.
Figure 8. Size distributions of HMW V compounds in asphaltenes ORCID
from CO4 at different dilutions in THF. Brice Bouyssiere: 0000-0001-5878-6067
Notes
The authors declare no competing financial interest.

■
A comparison of the LMW compounds with the V standards
in the chromatograms indicates that these compounds have a
MW that is typical of simple MPs and do not represent more ACKNOWLEDGMENTS
than approximately 22% of total V present in the crude oil. This The financial support of the Conseil Régional d’Aquitaine
result may explain the low percentage of the extraction of MPs (20071303002PFM) and FEDER (31486/08011464) is
by several methods cited in the literature.18 Remaining V is acknowledged.
7787 DOI: 10.1021/acs.energyfuels.7b00527
Energy Fuels 2017, 31, 7783−7788
Energy & Fuels Article

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7788 DOI: 10.1021/acs.energyfuels.7b00527

Energy Fuels 2017, 31, 7783−7788