Article

pubs.acs.org/EF

Molecular Representation of Petroleum Residues Using Fourier

Transform Ion Cyclotron Resonance Mass Spectrometry and
Conventional Analysis
Claudia X. Ramírez,*,† Juan E. Torres,*,‡ Diana Catalina Palacio Lozano,† Juan P. Arenas-Diaz,†
Enrique Mejia-Ospino,† Viatcheslav Kafarov,† Alexander Guzman,‡ and Jorge Ancheyta*,§
†
Universidad Industrial de Santander, Carrera 27 Calle 9, Bucaramanga, Santander 678, Colombia
‡
Ecopetrol S.A., Instituto Colombiano del Petróleo, Kilómetro 7 via Piedecuesta, Piedecuesta, Santander 4185, Colombia
§
Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas 152, Colonia San Bartolo Atepehuacan, México City 07730, México

ABSTRACT: A methodology for structurally representing the molecules of three Colombian vacuum residues (538+ °C) and
one Mexican atmospheric residue (300+ °C) is reported. Information obtained by Fourier transform ion cyclotron resonance
mass spectrometry coupled to positive electrospray ionization, negative electrospray ionization, and positive atmospheric
pressure photoionization sources and conventional standardized analytical methods was used for molecular representation of the
samples. The generation of molecules was performed by a Monte Carlo technique, obtaining a set of representative structures for
the global representation through attributes for each residue. The structural attributes considered are CH, CH2, and CH3 in
paraffinic chains, number of naphthenic rings, CH2 and CH naphthenic number of aromatic rings, aromatic carbon type, cata-
and peri-condensed carbons, number of sheets in asphaltenes, −SH, aromatic S (thiophene), aromatic N (pyridine and pyrrole),
and −NH2. Each attribute in the residues can be represented by a probability density function (PDF), which is optimized for the
purpose of adjusting the structures of residues and their composition to the experimental data. The PDFs for aromatics and
nitrogen and sulfur components were obtained by ultrahigh mass resolution data. As a result, 150 molecules per each residue
were obtained, and the mode of representation was single-feed (only one feed is characterized at the same time). The bulk
properties for each residue were in good agreement with the experimental structural information.

1. INTRODUCTION For instance Neurock 3 and Trauth 4 developed two

Currently, light crude oil reserves (that is, conventional oil) are
declining, and the future production scenarios show a higher
contribution of unconventional heavy crude oils to be used as
feed to refineries.1 These types of feeds are characterized by
their high density, high content of heteroatoms, high structural
complexity, and high component number. As a result of this
complex nature, there is a lack of detailed molecular
characterization of these heavy hydrocarbons. Thus, new
characterization techniques are required to provide detailed
information on complex feeds.
Standard techniques are not sufficient for proper character-
ization of heavy oils as a result of the complexity of most of the
components present in heavy cuts, such as vacuum residues.
In this regard, ultrahigh-resolution mass spectrometry,
Fourier transform ion cyclotron resonance mass spectrometry
(FT-ICR MS), emerges as a powerful technique that can
provide more detailed and vast information on the chemical
composition of very heavy and complex hydrocarbons that are
present in vacuum residues.2 The information obtained by this
technique depends upon the ionization efficiency of each
molecule in each ionization method employed. Therefore, a
structural characterization is obtained, but the exact composi-
tion of each molecule in the residue is unknown. Thus, it is
necessary to incorporate conventional and non-conventional
analyses to try to obtain a real characterization of this class of
feeds.
algorithms to generate model molecules from physical and
chemical properties of the oil, such as density, molecular weight
(MW), saturates, aromatics, resins, and asphaltenes (SARA)
analysis, true boiling point (TBP) distillation, hydrogen/carbon
ratio (H/C), nuclear magnetic resonance (NMR) spectroscopy,
and sulfur content. One algorithm minimizes the error between
measured and calculated properties by varying structures that
would represent the stream, which are obtained by stochastic
reconstruction. The estimation of the chemical properties of
each molecule is based on a group contribution, so that the
properties of the mixture are calculated; this reconstruction is
performed in an equimolar manner.5 The other algorithm also
minimizes the error between measured and calculated proper-
ties but, in this case, by performing an adjustment of the
molecule compositions by means of simulated annealing.
Hudebine and Verstraete6 employed two algorithms by
generating a set of model molecules from overall petroleum
analyses. The first one is based on stochastic reconstruction
(SR), and the second one is based on reconstruction by
entropy maximization (REM), this methodology was applied to
light cycle oil (LCO) and gas oils and subsequently extended to
heavy cuts such as vacuum gas oils7 and vacuum residues.8
Received: August 28, 2017
Revised: October 26, 2017
Published: October 31, 2017

© 2017 American Chemical Society 13353 DOI: 10.1021/acs.energyfuels.7b02507

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Figure 1. Molecular reconstruction algorithm.
De Oliveira et al.9 modified and applied the method
proposed by Hudebine and Verstraete6 in the molecular
representation of various vacuum residues from different
locations, with different characteristics. The objective in this
work was to evaluate the versatility of the methodology
proposed.
Zhang et al.10 proposed a methodology by sampling with
probability density functions (PDFs) and a juxtaposition of the
structural attributes for representing petroleum residues,
incorporating additional structural information inferred from
FT-ICR MS coupled to fragmentation by collision-induced
dissociation (CID) and knowledge of light petroleum fractions.
The aromatic ring configuration of cores was inferred from CID
FT-ICR MS results.
The basis for obtaining a set of representative structures
present in a hydrocarbon mixture is the global representation of
attributes, for instance, the number of aromatic rings, number
of side chains, number of cata- and peri-condensed carbons, etc.
Each attribute can be represented by a PDF.
The PDF of the attributes for each structure is built following
chemical rules to obtain the set of structures that better
represent the bulk properties of the residue under consid-
eration. Therefore, each density function employed for
representing a structural attribute allows for moving the
probability of occurrence of events of a random experience to
a numeric characteristic.
Incorporation of FT-ICR MS information in models based
on molecular representation can be an approach to improve
their representativeness. The data obtained by FT-ICR MS can
supply new structural parameters, such as the maximum
number of carbons, aromatic rings, and naphthenic longitude
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in each structure. Also, it can provide the PDFs for aromatics,
resins, and nitrogen and sulfur compounds.
In this study, three Colombian residues (538 °C+) and one
Mexican residue (300 °C+) were characterized by FT-ICR MS
and molecularly represented. The mode of representation was
single-feed (only one feed is characterized at the same time). A
total of 150 molecules per each residue were obtained. The
bulk properties for each residue were in good agreement with
the experimental structural information. The molecular
representation was evaluated studying the behavior of each
feed in a separation process with n-heptane in a commercial
process simulator.
2. MODELING APPROACH
2.1. Modeling of Structural Attributes. Any structure
present in the samples can be represented by their structural
attributes, such as the number of aromatic rings, number of side
chains, number of cata- and peri-condensed carbons, number
atoms of sulfur and nitrogen, etc. Each structural attribute can
also be represented by a PDF.
A PDF is defined by eqs 1 and 2, where f(x) is the PDF of
the variable x in the interval (0, 1).
0≤x≤1 (1)
∑ f (x ) = 1 (2)
According to the literature, the γ probability density function
(pi), which is defined by eq 3, with parameters α and γ > 0 and
the mean = μ, is the best PDF for representing the structural
attributes of heavy oil cuts. While a combination of γ,
exponential, and χ2 is more suitable for light cuts.11
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−(x1− γ )
if large numbers of random potential components are generated
[(xi − γ )(α − 1)e( θ
)
]
pi = (molecules).
Γ(α)θ α (3) Defining appropriate molecular attributes and developing an
adequate algorithmic construction are important aspects of this
where γ ≤ xi ≤ ∞, θ = μ − γ, σ = μ − γ, and γ = lower limit ≥ modeling technique. Once the molecules are represented by
0. appropriate structural attributes, the PDF corresponding to
Trauth4 and Campbell12 showed the characteristics that a these molecular attributes needs to be optimized to match the
PDF should have to be used for the representation of heavy experimental data. The first PDF for aromatic components was
cuts of petroleum. Good flexibility in its form for the obtained by positive electrospray ionization [ESI(+)]/negative
representation of any structural attribute is a main character- electrospray ionization [ESI(−)]/positive atmospheric pressure
istic. Thus, the M parameters of the distributions are important photoionization [APPI(+)]/FT-ICR MS information and was
for molecular representation (shape parameter “α, Mα” and assigned as a restriction of the objective function.
scale parameter “β, Mβ”). On this basis, the PDF parameters are With a representative set of molecules obtained by molecular
required for the representation of cuts of petroleum, which are representation, the next step is the estimation of properties.
unknown initially. Therefore, PDF parameters are to be These calculations were performed contribution methods. Each
assumed (initial guess) for representation and then adjusted method employed in this part was adjusted on the basis of its
to achieve a minimum error in the system. original correlation: density was calculated by the GCVOL-60
2.2. Molecular Representation of Petroleum Residues. method;14 boiling point was calculated by method of Retzecas
Two algorithms, one for obtaining molecules (Monte Carlo) et al.;15 fusion solid properties were calculated by the method
and another for adjustment of their compositions (simulated of Coutinho et al.;16 fusion heat was calculated by the
annealing) are employed in the molecular representation of correlation of Won;17 refractive index was calculated by the
residues using the same objective function (eq 4). The estimation of Satou et al.;18 and critical properties were
molecular representation algorithm is shown in Figure 1. calculated by the method of Riazi.19
⎧⎛
In the first algorithm (Monte Carlo method), the error
≠ fractions ⎞
⎪⎜ ∑i=1 (TBPiexp − TBPicalc) ⎟ between the predicted and calculated properties is minimized,
objective function(P) = minimize⎨⎜ ⎟ changing the M parameters of the PDF, and the molecules
⎪⎜ A ⎟
⎩⎝ ⎠ obtained have an equimolar composition. With the second
⎛ (ρ − ρ ) ⎞ ⎛ (PM − PM ) ⎞ algorithm, simulated annealing, the molar fraction of molecules
+ ⎜⎜ ⎟⎟ + ⎜⎜
exp calc exp calc
⎟⎟ in the feed is adjusted to minimize the error between
⎝ B ⎠ ⎝ C ⎠ experimental and calculated properties, without changing the
⎛ (wax exp − wax calc) ⎞ structures obtained in the first step.
+ ⎜⎜ ⎟⎟
⎝ D ⎠ The structural attributes considered in this work are CH,
⎛ ≠ components ⎞ CH2, and CH3 in paraffinic chains, number of naphthenic rings,
⎜ ∑i=1 (SARA iexp − SARA icalc) ⎟ CH2 and CH naphthenic number of aromatic rings, aromatic
+⎜ ⎟ carbon type C and CH, cata- and peri-condensed carbons,
⎜ E ⎟
⎝ ⎠ number of islands in asphaltenes, −SH, aromatic S (thiophene),
⎛ ≠ distributions ⎞ aromatic N (pyridine and pyrrole), and −NH2.
⎜ ∑i=1 (arom dist iexp − arom dist icalc) ⎟
SARA analysis helps classify the structural attributes of the
+⎜ ⎟
⎜ F ⎟ vacuum residue molecules. Based on the considerations
⎝ ⎠
proposed by de Oliveira et al.,20 saturate fractions without
⎛ ≠ distributions ⎞ heteroatoms are composed of n-paraffins and naphthenes
⎜ ∑i=1 (massesiexp − massesicalc) ⎟
+⎜ ⎟ (cyclohexane rings and aliphatic side chains). The aromatic
⎜ G ⎟ fraction is composed by aromatic rings, saturate rings, and
⎝ ⎠
⎛ ≠ tipos ⎞ aliphatic side chains. As a result of their similar structures, the
⎜ ∑i = 1 (NMR exp − NMR icalc) ⎟ resin fraction is just like the aromatic fraction but it contains
+⎜ ⎟
⎜ E ⎟ heteroatoms of sulfur and/or nitrogen. Asphaltenes are
⎝ ⎠ constructed identically to resin molecules with the addition of
⎛ (Sexp − Scalc ) ⎞ ⎛ (Nexp − Ncalc basic) ⎞ a degree of polymerization and cannot have a molecular weight
+ ⎜⎜ ⎟⎟ + ⎜⎜ basic ⎟
⎟
⎝ H ⎠ ⎝ I ⎠
below 400 g/mol.
The calculation of molecular representation begins with an
⎛ (Nexp − Ncalc ) ⎞ ⎛ (xC − xC ) ⎞
+ ⎜⎜ total total
⎟ + ⎜⎜ exp calc
⎟⎟ estimation of the objective function, which employs a set of
⎟
⎝ J ⎠ ⎝ H ⎠ initial PDF parameters estimated from the information
⎫ obtained by FT-ICR MS. For the case of aliphatic structures,
⎛ ∑M parameters (PDF − PDF ) ⎞⎪
⎜ i=1 iexp icalc ⎟⎪ these distributions were initialized randomly.
+ ⎬
⎜ K ⎟⎪
⎝ ⎠⎪
⎭ (4) 3. EXPERIMENTAL SECTION
3.1. Materials. Three Colombian vacuum residues (538 °C+) from
The initial molecular reconstruction of feeds from the
different geographical areas, named hereafter VR-T, VR-P, and VR-S,
information obtained by the characterization techniques uses and one Mexican atmospheric residue (300 °C+), named hereafter
Monte Carlo simulation, which is a quantitative technique AR-MX, were used as samples, which were characterized and
based on statistic and computer simulations to mimic the represented using model molecules.
behavior of non-dynamic random real systems,13 using 3.2. Conventional Analysis. The residue samples were
mathematical models. This technique is much more accurate characterized by the following bulk properties: density was measured

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by means of a digital densimeter (ASTM D4052); molecular weight Table 1. Conventional Analysis for Residue Samples
was measured by vapor pressure osmometry (VPO, ASTM 2503);
weight percentages of C, H, and N were measured by elemental property VR-T VR-P VP-S AR-MX
analysis (ASTM D5291); SARA weight fractions were measured by density (g/cm3) 1.0337 1.0251 1.0687 1.0336
SARA compositional analysis (ASTM D2007); distillation curve was SARA compositional analysis
measured by the high-temperature simulated distillation (HTSD) saturates (wt %) 14 11 3 21
method (ASTM D7169); wax content was measured by the UOP 46
aromatics (wt %) 36 46 36 30
method; carbon residue was measured by the micro method (ASTM
resins (wt %) 44 37 34 24
D4530); and aromatic and aliphatic carbons were measured by 13C
NMR (standard procedure in house). asphaltenes (wt %) 6 6 27 25
3.3. Non-conventional Analysis. The non-conventional analyses elemental analysis
used for the characterization were the ultrahigh mass resolution carbon (fraction) 0.86 0.86 0.84 0.82
spectrometry, a combination of ESI(+), ESI(−), and APPI(+) FT-ICR nitrogen (fraction) 0.009 0.009 0.007 0.004
MS. FT-ICR MS analyses were performed using a 15 T SolariX FT- sulfur (fraction) 0.023 0.018 0.021 0.057
ICR mass spectrometer of Bruker Daltonics (Billerica, MA, U.S.A.). carbon residue (wt %) 18.8 19.5 35.1 23.2
Nitrogen was used as the drying and nebulizing gas. All prepared waxes (fraction) 0.009 0.009 0.006 0.007
samples were directly injected with a syringe pump. number-average 784 809 871 704
For APPI, samples were diluited to 0.1 mg/mL using toluene. The molecular weight (g/mol)
nebulizing temperature was 300 °C at a constant pressure of 0.7 bar. high-temperature simulated distillation
The drying temperature was 200 °C at a flow rate of 4.5 L/min. An ion 0.5 wt % (°C) 439 448 461 438
accumulation time in the collision cell of 0.010 s was set, which was
5 wt % (°C) 504 519 532 538
followed by a time of flight of 0.1 s to transfer the ions to the ICR cell.
For ESI, samples were diluted in 40:60 (v/v) toluene/methanol 50 wt % (°C) 674 670 730 800a
solution to yield a 0.1 mg/mL solution. Acetic acid was added (10 μL 90 wt % (°C) 824a 834a 863a 1023a
to each 1 mL of sample solution) to facilitate protonation of basic 99 wt % (°C) 909a 927a 947a 1141a
compounds by positive ion mode, and for negative ion mode, nuclear magnetic resonance (NMR)
ammonium hydroxide was added (10 μL to each 1 mL of sample 13
C NMR aliphatic CH3 0.12 0.12 0.11 0.10
solution) to promote deprotonation of acidic compounds. In all (fraction)
13
spectra, time-domain transient signals were accumulated and averaged C NMR aliphatic CH2 0.57 0.54 0.51 0.56
(100 scans) to enhance the signal-to-noise ratio of each spectrum. and CH (fraction)
13
C NMR aromatic C 0.23 0.25 0.28 0.26
(fraction)
4. RESULTS AND DISCUSSION 13
C NMR substituted 0.08 0.09 0.10 0.08
4.1. Characterization of Residues. The conventional aromatic C (fraction)
characterization of residues is given in Table 1. According to a
Temperatures calculated using ASTM distillation probability curves.
the HTSD experimental data, the initial boiling point for all
residues is higher than 430 °C, which indicates that the
structures present in these samples have more than 20 carbon ESI(+)/ESI(−)/FT-ICR MS. The aim of using multiple
atoms. This information was further confirmed by the results ionization methods for sample characterization was to provide
obtained by FT-ICR MS. detailed information about of its composition and obtain
The vacuum residues have such high boiling points that it is distributions employed in molecular representation.
not possible to recover in the highest boiling fractions by FT-ICR MS provides qualitative information from 12
HTSD; therefore, the complete distillation curve of vacuum carbons onward. The FT-ICR MS information shows the
residues cannot be obtained. To acquire a complete description presence of a large amount of classes defined by the interaction
of the sample as function of the boiling point, the available data of functional groups. By all structures in each class, the
must be fitted to a continuous curve that represents the limits following parameters are obtained: molecular formula, intensity
of samples studied to a final boiling point, so that with this of ionization, distribution of number of carbons, and double
approach the tendency of the distillation curve, can be bond equivalent (DBE, according to eq 5, where c, h, and n are
calculated, and the values be compared to the results obtained the numbers of carbon, hydrogen, and nitrogen atoms,
by molecular representation. The boiling points over 750 °C respectively). DBE is defined as the number of rings plus the
were calculated through the probability extrapolation meth- number of double bonds in a chemical structure. The degree of
od.21−23 aromaticity of a compound can be related directly to its DBE
The data of non-conventional analysis, obtained by ultrahigh value.
mass spectrometry, were processed and analyzed. The complex
DBE = c − h/2 + n/2 + 1 (5)
feeds studied were directly related to the class and number of
components that make up this type of residue. Figure 2 A set of parameters and restrictions has been determined for
summarizes the results of characterization with FT-ICR MS for molecular representation of the four samples with FT-ICR MS
each residue in terms of the percentage of each species detected information. Each detected class contains data of relative
in each ionization method for class evaluation and used as input abundance, molecular formula, and molecular weight. Data
information for the molecular representation (the classes used to obtain the DBE for each compound were identified
shown have a percentage higher than 1, in relative abundance). within each class by the method of ionization. On the basis of
It is appreciated because of how some classes were this information, the PDFs for aromatic, sulfur, and nitrogen
characterized by two or three ionization methods. For example, compounds were obtained by relating the relative abundance
HC is the class that contains only carbon and hydrogen atoms and DBE in the assessed class (the PDF was obtained for sulfur
and was detected by APPI(+)/FT-ICR MS. The N1 class, apart by relating all sulfur-detected classes in a method, with the same
from containing carbon and hydrogen atoms, includes a manner for nitrogen PDF). An example is shown in Figure 3; in
nitrogen atom in each structure, detected by APPI(+)/ this case, the PDFs for aromatics were obtained from HC class
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Figure 2. Percentage of detected species by the ionization method for class.
Figure 3. Information obtained by FT-ICR MS: (blue circles) γ distribution and (red triangles) APPI(+)/FT-ICR MS distribution.
distributions relating the relative abundance and its DBE. Also,
the maximum number of carbons per molecule and the
maximum number of aromatic rings were the restrictions
established with FT-ICR MS information (Figure 4).
4.2. Molecular Representation of Petroleum Residues.
The molecular representation by structural attributes was
developed by taking into account a set of features. First, the set
of molecules must represent the feed and its behavior into the
system. Second, the generated structures should be appropriate
for their use in process simulators and economic evaluation
tools. Additionally, the required time for central processing unit
(CPU) usage in molecular representation must be affordable.
Therefore, it was necessary to analyze each of the variables
mentioned above. First, the maximum number of components
supported by commercial simulators was examined. In the
particular case of the PRO/II process simulator, the limits for
the use of resources are according to each category,24 number
of streams, components, and units, among others. A total of
300 components are the maximum number of structures that
can be used in this simulator. Accordingly, the number of
structures that characterizes each sample is restricted to the
maximum number of molecules that can be supported and
employed in the simulator as a result of the future applications
for these as an input stream in reaction and separation
compositional models. It is appropriate to clarify that, for
reaction systems, the number of structures present can be
tripled as a result of the present reactions, and as previously
mentioned, a large number of molecules cannot be supported
in a commercial simulator, with all of the criteria set assessed,
so that a set of 150 molecules for each sample evaluated was
obtained.
With the number of molecules sectioned, the next step is to
obtain the PDF parameters by FT-ICR MS. Each pair of
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parameters, in each distribution used, was generated for an
ionization method: the PDF parameters for non-basic nitrogen
compounds were obtained from ESI(−)/FT-ICR MS; the PDF
parameters for basic nitrogen compounds were obtained from
ESI(+)/FT-ICR MS; and the PDF parameters for sulfur
compounds, aromatic distributions, and aromatic distributions
in resins were obtained from APPI(+)/FT-ICR MS. These
values are shown in Table 2. The molecular representation uses
up to 76 distribution parameters, and the first 18 are used in the
generation of saturated aromatic structures and resins. The
other 58 parameters are used for the generation of asphaltenes,
with the following restrictions: maximum of seven islands
present in the asphaltene archipelago type; 10 aromatic rings
present in any aromatic structure; and a maximum of 80
carbons presents in other structures. The restrictions were
obtained from the FT-ICR MS information. Each island or
archipelago have its own set of distributions and may be
different from the other islands and/or archipelagos.
Before generation of the molecules using all of the
information obtained, incorporating the information on
conventional analytical, a molecular representation was
generated having the PDF parameters as unique input values
(Table 2) and constraints obtained with FT-ICR MS
information (without conventional analytical information),
with the aim to analyze system behavior. It was observed that
SARA values obtained for the representation of each sample
were close to the experimental values (R2 > 0.98) The
comparisons are shown in Figure 5. This indicates that the PDF
employed is suitable for the reconstruction of molecules.
The molecular representation using FT-ICR MS information
and conventional analysis was applied to three vacuum residues
and one atmospheric residue, using the previously described
distribution and molecular rule scheme. A set of 150 molecules
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Figure 4. Plots of the number of carbons versus DBE for classes obtained by APPI/ESI(+)/ESI(−)/FT-ICR MS employed in molecular
representation: (A) AR-MX, (B) VR-T, (C) VR-P, and (D) VR-S.

Table 2. Experimental Parameters of PDFs Obtained by FT- normally reports high values of molecular weight for samples
ICR MS with a high content of asphaltenes. The high values of
molecular weight obtained with VPO are attributed to
PDF AR-MX VR-T VR-P VR-S
aggregation of asphaltenes in the employed solvent (toluene).25
α, non-basic nitrogen compounds 4.950 0.120 5.200 5.000
To minimize the impact of using values of molecular weight
β, non-basic nitrogen compounds 0.200 0.800 0.190 0.200
determined by VPO, it was considered as a not fixed property,
α, basic nitrogen compounds 5.100 0.600 5.100 4.700
which means that it was included as a comparative parameter in
β, basic nitrogen compounds 0.205 1.970 0.200 0.280
the objective function.
α, sulfur compounds 4.700 0.120 5.200 4.700
The predictions of properties for VS-S and VR-T are worse
β, sulfur compounds 0.250 1.000 0.310 0.290
α, aromatic rings 3.250 5.700 4.300 5.000
than those for AR-MX and VR-P, but in all of the cases, they
β, aromatic rings 0.850 0.700 0.830 0.800
presented low absolute errors, which indicates that a good set
α, aromatic rings in resins 7.700 8.000 10.200 10.600
of structures was selected. The difference in predictions of
β, aromatic rings in resins 0.550 0.500 1.460 0.530 properties of VR-S/VR-T and AR-MX can be due to the
distribution of the number of molecules per class in the set of
150, which is directly linked to their SARA. It is possible that
for each sample was generated. The absolute error between more structures in a class are needed than others to obtain a
calculated and experimental properties for each set of molecules better prediction of bulk properties, in certain feeds; for
that represents the samples is shown in Table 3. This example, an increase of the number of saturate molecules and a
information provides evidence that molecular representation decrease of the number of aromatic structures in the feed.
depicts quite well most of the information supplied in the However, this condition increases the complexity of the system
proposed model. In this reconstruction, the molecular weight and will require new optimization approaches.
was the property that presented the higher error. The method Table 4 shows the 10 first molecules and their compositions
of VPO was used to obtain the molecular weight, which generated by molecular representation for the four residues.
13358 DOI: 10.1021/acs.energyfuels.7b02507
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Figure 5. Parity graphs: (A) parameter PDF and (B) SARA.
Table 3. Absolute Error between Calculated and Experimental Properties
Some of these structures have 10 or more naphthenic rings but
no more than 10 aromatic rings, which have been validated with
FT-ICR MS information. In all of the cases, most of the
structures were different.
With all of the information obtained in the characterization
of the residues with conventional and non-conventional
analytical tests and with the result of their representation by
structural groups (Table 4 and Figure 6), it is possible to
describe the AR-MX sample as one that presents the highest
degree of aromaticity and condensation of asphaltenic
structures, which have short lengths in their alkyl chains.
With regard to the number of aromatic rings present in the
compounds of the aromatic and resin fractions, they have
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mostly low aromaticity and degree of condensation but longer
length in side chains associated with these species.
Concerning the individual composition of each feed, the
structures that possess greater composition correspond to
resins and naphthenes.
VR-P has the highest aromaticity and CH2 lengths in the
aromatic and resin fractions compared to the other residues,
and this fraction has a low degree of condensation. This sample
was found to have asphaltenes of continental and archipelago
types, with distributions shown in Figure 6 and hereafter VR-
P(1), VR-P(2), and VR-P(3). Most structures present in the
asphaltenic fraction are archipelago of low aromaticity and
degree of aromatic condensation. The molecules with the
highest individual composition are aromatics and resins.
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Table 4. Main Molecules and Compositions Generated by Molecular Representationa
a
★, asphaltene molecules; X, composition.
VR-S presented the lowest degree of aromaticity and
cycloaliphaticity in the aromatic and resin fractions. This
residue also has the lowest number of naphthenic rings in the
saturate fraction. The molecules with the highest individual
composition are of the type of resins and asphaltenes.
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VR-T has greater degree of condensation in the fraction of
aromatics and resins. The molecules with the highest individual
composition are aromatics and resins.
4.3. Evaluation with a Commercial Simulator. After the
representative structures were obtained using molecular
representation with conventional properties and FT-ICR MS,
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Figure 6. Distributions for structural classes in feeds evaluated obtained in the molecular representation.
an evaluation based on a liquid−liquid separation system was
carried out. The liquid−liquid equilibrium depends consid-
erably upon the structure of the components present in the
feed.26 Each residue is put in contact with a heptane solvent,
which promotes the separation of the heavy fraction (pitch)
from the deasphalted oil (DAO). The degree of separation of
the DAO−pitch mixture was evaluated using different solvent/
feed ratios.
For the operating conditions of the proposed system (1 atm
of pressure and 30 °C), the modified UNIFAC thermodynamic
model was used. The model was developed in SimSci PRO/II,
version 9.1.
A low solubility with polyaromatic hydrocarbons and heavy-
resin hydrocarbons and a high solubility with saturate
hydrocarbons were found. This behavior is shown in Figure
7. In all cases, if the solvent/feed ratio increases, the percentage
of DAO increases and the percent of pitch decreases. For the
13361
Article
case of VR-P, as a result of its characteristics, low percentage of
asphaltenes and most of the structures present in the asphaltene
fraction of archipelago type of low aromaticity and degree of
aromatic condensation, the percentage of pitch obtained was
low. Wauquier27 and Torres and Picón28 reported that the
selectivity of a solvent may vary depending upon the feed/
solvent ratio in the deasphalting process (Figure 8). If this ratio
increases, the selectivity toward asphaltene compounds also
increases. The same behavior was observed in the evaluation for
residues evaluated.
5. CONCLUSION
Three Colombian vacuum residues and one Mexican
atmospheric residue were characterized and molecularly
represented. A set of 150 molecules per each residue was
obtained. The bulk properties of residues were in good
agreement with the experimental structural information. The
DOI: 10.1021/acs.energyfuels.7b02507
Energy Fuels 2017, 31, 13353−13363
Energy & Fuels Article

Figure 7. Flowsheet and behavior of products (pitch and DAO) in the separation process with heptane.

SARA analysis of petroleum residues can be calculated from

the distribution parameters obtained by FT-ICR MS and the
molecular representation methodology. It can be concluded
that the maximum number of aromatic rings present in
asphaltene structures is 10.
The asphaltene structures present in the vacuum residues are
continental and/or archipelago type; in the case when the two
types of asphaltenes are present always as a type, it is one that
predominates.

■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: claudia.ramirez2@correo.uis.edu.co.
*E-mail: juan.torres@ecopetrol.com.co.
*E-mail: jancheyt@imp.mx.
ORCID
Claudia X. Ramírez: 0000-0001-8710-8564
Notes
The authors declare no competing financial interest.

Figure 8. Influence of the feed/solvent ratio on extraction selectivity.
This graphic was adapted from Wauque.27
representation evaluated the behavior of each residue in a
separation process with n-heptane in a commercial process
■ ACKNOWLEDGMENTS
The authors thank the Colombian Institute of Petroleum (ICP)
for financial support and the Mexican Institute of Petroleum
(IMP) for providing the AR-MX sample data. The develop-
ment of this work was supported by the Research Agreement
No 5211770 ACTA 2 between Universidad Industrial de
Santander and ECOPETROL S.A - ICP. To COLCIENCIAS
for the graduate fellowships of Diana Catalina Palacio Lozano
and Juan P. Arenas-Diaz.

■
simulator.
APPI(+)/ESI(+)/ESI(−)/FT-ICR MS information was used
for molecular representation, obtaining parameters of PDF for NOMENCLATURE
attributes, such as the distribution of aromatics and sulfur and APPI(+) = positive atmospheric pressure photoionization
nitrogen compounds. Also, restrictions, such as the maximum AR = atmospheric residue (300 °C +)
number of carbons per molecule and the maximum number of DAO = deasphalted oil
aromatic rings, were established. DBE = double bond equivalent
13362 DOI: 10.1021/acs.energyfuels.7b02507
Energy Fuels 2017, 31, 13353−13363
Energy & Fuels Article

ESI(−) = negative electrospray ionization (17) Won, K. W. Fluid Phase Equilib. 1986, 30, 265−279.
ESI(+) = positive electrospray ionization (18) Satou, M.; Yamaguchi, H.; Murai, T.; Yokoyama, S.; Sanada, Y.
FT-ICR MS = Fourier transform ion cyclotron resonance Sekiyu Gakkaishi 1992, 35 (6), 466−473.
mass spectrometry (19) Riazi, M. R. Characterization and Properties of Petroleum
Fractions, 1st ed.; ASTM International: West Conshohocken, PA,
H/C = hydrogen/carbon molar ratio 2005.
HTSD = high-temperature simulated distillation (20) de Oliveira, L. P.; Vazquez, A. T.; Verstraete, J. J.; Kolb, M.
MW = molecular weight Energy Fuels 2013, 27 (7), 3622−3641.
N = nitrogen (fraction) (21) Whitson, C. H. SPEJ, Soc. Pet. Eng. J. 1983, 23 (4), 683−694.
NMR = nuclear magnetic resonance (22) Meirelles, L. B.; Chrisman, E. C. A. N.; de Andrade, F. B.; de
PDF = probability density function Oliveira, L. C. M. Int. J. Chem., Mol., Nucl., Mater. Metall. Eng. 2017, 11
pitch = heavy product after deasphalting (3), 237−241.
S = sulfur (fraction) (23) Handbook of Petroleum Processing, 2nd ed.; Treese, S. A., Pujad,
SARA = saturates, aromatics, resins, and asphaltenes P. R., Jones, D. S. J., Eds.; Springer: Cham, Switzerland, 2015; Vol. 1,
TBP = true boiling point DOI: 10.1007/978-3-319-14529-7.
(24) Invensys Systems, Inc. SimSci-Esscor PRO/II 9.1 Getting Started
VPO = vapor pressure osmometry
Guide; Invensys Systems, Inc.: Lake Forest, CA, 2011.
VR = vacuum residue (538 °C +) (25) Ancheyta, J.; Trejo, F.; Rana, M. S. Asphaltenes: Chemical
C = carbon (fraction) Transformation during Hydroprocessing of Heavy Oils, 1st ed.; CRC
pi = γ probability density function Press (Taylor and Francis Group): Boca Raton, FL, 2010; DOI:
α = shape parameter 10.1201/9781420066319.
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ρ = density Wiley & Sons, Inc.: Hoboken, NJ, 2006.
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Ed.; Editions Technip: Paris, France, 2000.
Subscripts (28) Torres, J. E.; Picón, H. J. Ing. Quim. 2012, 44 (506), 52−56.
exp = experimental data
calc = calculated data

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13363 DOI: 10.1021/acs.energyfuels.7b02507

Energy Fuels 2017, 31, 13353−13363