Influence of Hydrocarbon Distribution in Crude Oil

and Residues on Asphaltene Stability†

Sharen Putri Nursalil
Petroleum Engineering Department, Trisakti University, Jakarta, Indonesia

Abstract
Flow assurance problems caused by asphaltene deposition are
related to the solvent quality of the surrounding medium rather than
the amount of asphaltenes. Traditionally, solvent quality has been
focused on resins, which are the most similar fraction to asphaltenes,
in terms of aromaticity and polarity. Still, no answer is available to
the question whether resins (defined as the soluble fraction in n-
heptane but insoluble in n-pentane) act as co-solvents or have a more
critical interaction with asphaltenes.
This workdeals with the study of asphaltenes stability in two
South American crude oils and their distilled residues (190þ, 370þ,
and 565þ). The total amount of asphaltenes for each sample has been
determined by the IP- 143 standard method. When asphaltene
percentage is normalized to whole crude oil using the true boling
point (TBP) data from distillation following the ASTM D-2812
standard, a shift to a greater asphaltene mass is observed when light
cuts are removed. Stability of asphaltenes and aggregation kinetics
have been assessed by focused-beam laser reflectance measurements
(FBRMs).
Differences between each crude oil and its residues are observed.
FBRM evidence has been confirmed by transmittance analysis using
a Turbiscan device. Resins (defined as C5-insoluble and C7-soluble)
and an aromatic compound [R-methyl- naphthalene (RMN)] have
been doped into the original crude, to assess their effect on stability.
Results have shown that the C5-C7 fraction increases asphaltene
stability to a similar extent as a diaromatic molecule, such as RMN.
All of this evidence may indicate that the effect of C5-C7 resins and
diaromatic addition and the removal of light ends have a similar
impact on asphaltene stability, supporting the belief that the solvent
quality as a whole rules asphaltene behavior.
Keyword : crude oil, , supporting the belief that the solvent quality
Introduction
The asphaltene fraction is traditionally defined as a solubi- lity class, because it
comprises molecules that are soluble in toluene and insoluble in a light n-alkane
(such as heptane).1,2 This definition, apart from creating significant confusion in
the literature,3 leads to the fact that asphaltene problems in upstream operations
are not correlated with the amount of asphaltenes. In fact, it is more common to
observe asphaltene plugging with light undersaturated oils4 rather than with
heavy aromatic crudes with high asphaltene concentrations (Boscan,
Venezuela).5 This indicates that the quality of the surrounding medium is more
relevant for asphaltene phase equilibrium than the actual amount of molecules
that would precipitate upon heptane addition.
If one uses saturates, aromatics, resins, and asphaltenes (SARA) terminology,
solvent quality is related to the relative amount of saturates, aromatics, and
resins; saturates worsen the capacity of keeping asphaltene nanoaggregates
stable, while aromatics and resins improve the quality of the medium. There is a
significant controversy on the role of resins on asphaltene stability, as recently
reviewed by Goual.6 Resins represent the transition between the nonpolar
medium (saturates and aromatics) and the polar asphaltenes. Histori- cally, the
depiction of the asphaltene state in crude oil included a layer of resins surrounding
asphaltene colloids, such as in the Pfeiffer and Saal model.7 Several
thermodynamic models have been derived from this kind of interaction between
asphal- tenes and resins.8,9 Even if significant concerns10,11 have been raised
against a depiction such as that proposed by Pfeffier and Saal, there are many
references in the literature that demonstrate the interaction between resin and
asphaltene fractions in model solvents12,13 and also inside crude oil.14 Still, no
answer is available to the question about how critical this interaction is. Thatis to
say, it is unclear whether resins act as co-solvents, increasing the solvent quality
similar to aro- matics, or play a critical role in the formation and stability of
asphaltene nanoaggregates.
To complicate matters more, research on this issue is enormously impeded by
the fact that no unified definition is currently used to separate resins. For
instance, Shaw and co-workers have shown that nanoaggre- gates in Maya oil
and Athabasca Bitumen are mainly formed by molecules that fit the C5-
insoluble definition. The role of resins in nanoaggregate formation is clearly
biased by the criteria used to delimit asphaltene and resin fractions. In fact, it has
been proposed to merge resins and asphaltenes into one single fraction
(associating material). This view is more coherent with the idea of having a
continuum of molecules in crude oil.
This work explores the effect of different families of com- pounds on asphaltene
 stability and destabilization kinetics. Onset and the asphaltenes aggregation
kinetics near the onset were determined by focused-beam laser reflectance
measure- ments (FBRMs). Moreover, stability is also assessed by means of the
separability number (SN), obtained in Turbiscan experiments.
The effect of the loss of light ends (associated to mainly saturate compounds)
is addressed by analyzing the stability behavior of crude oil residues (190þ, 370þ,
and 565þ). On the other hand, resins (defined as C5-insoluble and C7-soluble) and
aromatics [represented by a diaromatic compound, R-methyl-naphtalene (RMN)]
are evaluated by doping the crude with increasing amounts of these compounds

Experimental Section
Samples. Two crude oils and their 190þ, 370þ, and 565þ distillation residues were
studied. Table 1 shows the density, source, and nature of the different oils tested.
Crude oil A has shown to be stable from the point of view of asphaltene deposi-
tion in upstream operations, whereas crude oil C showed deposition problems.
Reagents. n-Heptane reagent-grade (density, 0.68 g/cm3; 99% pure) was used as
received. Toluene reagent-grade ACS ISO (density, 0.87 g/cm3; 99.9% pure) was
used as received. R-Methyl-naphthalene (tagged as RMN in this work, 97%) was
used as received. All of the reagents have been supplied by Scharlab S.L.
Asphaltene Separation. The amount of asphaltenes of crude oils and their
residues were obtained by means of the IP-143 standard method.1 In this
procedure, an excess of n-heptane is added to precipitate asphaltenes and the
insolubles are sepa- rated by filtration. Once solids are isolated, they are first
washed with heptane and then toluene at their respective boiling points in a Sohxlet
extractor. Evaporation of toluene permits the quantification and isolation of
asphaltene solids.
Resin Separation. Resins are defined in this work as the family of compounds that
are soluble in heptane and insoluble in n-pentane. The authors are aware of the
fact that this limits

Table 1. Characteristics of Crude Oils Used in This Study

crude oil °API source classificationa

A 21 South naphthe
America nic
C 34 South paraffini
America c
a Determined through KUOP measurements
the resin definition to a fraction of the amount of resins obtained by the ASTM
standard (D-2007).15 The idea was to assess the influence of the molecules that
are more similar to asphaltenes, which are believed to be comprised of the
fraction between C5 and C7.
Laser-Reflectance Measurements. A FBRM S400A LASEN- TEC
manufactured by Mettler-Toledo (Columbus, OH) was employed. The FBRM
instrument operates by scanning a highly focused laser beam at a fixed speed
across particles in suspen- sion. As the solution is stirred, particles move along
with the fluid. When a particle crosses the area where the beam is focused, it
reflects part of the light. The duration of the signal of the backscattered light
from these particles renders a char- acteristic measurement of the particle
geometry, i.e., a chord. The number of recorded chords is reported as counts.16,17
FBRM experiments with crude oils and residues were per- formed at 60
°C in a close system. Working at this temperature is necessary to avoid wax
particle interferences, to reduce residue viscosity, and to enhance mixing with
heptane. In a typical FBRM experiment, crude oil was introduced in a glass
beaker and heated to the test temperature. The stirring rate was maintained at
400 rpm. Titration was performed using a dosing pump until the onset n-
heptane/oil ratio (Ronset) was reached. Volumetric steps of 0.1 mL of n-heptane/g
of oil were used. Each injection was carried out after a stabilization time of 20
min. The chord length distributions (CLDs) were recorded every 10 s in 120
channels of sizes up to 30 μm linear scale. Following the process exposed in
previous works,16,17 the CLDs were trans- formed into particle size distributions
(PSDs), with the model for spherical particles developed by Hukkanen and
Braatz.18
Aggregation kinetic studies were carried out with a 10% excess of n-
heptane with respect to the onset value. This criterion was taken to increase
kinetics with respect to the slow rates observed at the onset. When the
aggregation kinetics was expressed as a percentage of the onset volume, it was
considered that all samples were subjected to the same supersaturation.
Figure 1 shows an illustration of the aggregation rate at the onset and at a
greater supersaturation (10% in volume of heptane).
Turbiscan Measurements. Stability of a crude oil sample is determined by
determining the SN, following ASTM standard D-706118 with a Turbiscan
(TMA 2000 heavy fuel, for- mulaction). In these experiments, excess heptane
is added to a mixture of crude oil and toluene. All asphaltenes are forced to
precipitate, and the particle size is assumed to be related to asphaltene stability.
Sedimentation is monitored for 15 min from the bottom of the test tube to the
top, by means of transmittance scans every minute (wavelength of 850 nm).
Unstable oils form large asphaltene particles that sediment quickly, while stable
oils form small aggregates that show small changes in transmittance. SN is
defined as the standard deviation of the average transmittance. Values lower
than 5 indicate high oil stability, while values greater than 10

Figure 1. Aggregation kinetics at the onset and at a 10% supersaturation with

crude A.
 Figure 2. Illustration of a Turbiscan experiment to obtain the SN.
indicate that the asphaltenes are unstable. Figure 2 displays transmittance signal
as a function of the probe length, recorded after 1 min (beginning of test) and at
the end of a 15 min experiment.

Results and Discussion

Asphaltene Content. The total amount of asphaltenes in crude oils and their
residues was determined through the IP- 143 procedure. From true boiling point
(TBP) curves of crude oils obtained in a controlled vacuum distillation following
the ASTM D-2892 standard, the relative weight of residue fractions to crude oil
weight was calculated. This value has allowed for normalization of the IP-143
asphaltene percentage of each sample to total crude oil to determine the influence
of the light ends on asphaltene content. Table 2 shows the percentage of weight
of each residue with respect to crude oil, the IP-143 content of asphaltenes, and
the normalized amount.
Results show that crude oil A has similar asphaltene content as crude oil C.
The amount of IP-143 asphaltenes rises significantly as more light compounds
are removed from crude A. On the other hand, the effect in crude C is minimal
once asphaltene content has been normalized. Figure 3 shows the influence of the
surrounding medium on the amount of asphaltenes that come out of the solution.
Crude A yields more asphaltenes when light ends are removed; however, this
behavior is not reproduced when a more paraffinic crude, such as crude C, is used.
Asphaltene Onset by FBRM. The laser reflectance techni- que was used
(following the procedure exposed in the Experimental Section) to determine the
asphaltene onset at 60 °C for each sample. Table 3 shows the results obtained.
For crude oil A, a shifting to a higher value of onset is observed when light ends
are eliminated; once lighter com- pounds are removed, asphaltene stability
determined by onset studies is held, although heavier compounds have been taken
out. For crude C, the displacement to higher values of Ronset, related to more stable
asphaltenes, occurs when larger quantities of lighter compounds are eliminated
from crude oil (65%). The different nature of crudes (crude A is naphthenic, and
crude C is paraffinic) can explain this behavior. Moreover, crude C is more
unstable that crude A, because the onset is lower in all cases, despite the initial
similar content.
Asphaltene Aggregation Kinetics by FBRM. A kinetic study was carried
out to determine asphaltene aggregation behavior. The criterion of 10% excess
heptane was mod- ified for onset values below 1 mL/g, because 10% was not a
significant increase if the onset was around 0.2 mL/g. In these cases, one addition
of 0.1 mL/g was made to achieve the desired n-heptane excess, i.e., 10% excess.
Results for both crudes are shown in panels a and b of Figure 4. The number of
counts in the kinetic study is normalized for all samples to the maximum value
measured in the interval showed in the figure. For crude A, it is observed that the
kinetics are slower as light ends are removed, leading to greater times until final
particle sizes are reached; the slow kinetic growth indicates that asphaltenes are
more stable in residues than in crude oil. Crude C does not show any trend.
With respect to average size distribution, minimal differ- ences have been
observed in all samples as a function of time. The number of particles increases,
but the distributions are centered on the same values, as displayed in Figure 5
(190þ residue of crude A).

Figure 7. Results of stability experiments by ASTM

D-7061: (a)
crude A and (b) crude C.
 Table 2. Yield to Crude Oil for Residues, Asphaltene Content Determined by
IP-143, and Normalized to Crude Oil Asphaltenes

crude weight/c IP-143 normalized

oil/ rude asphaltene to crude
resid weight s (%) asphaltenes
ues (%) (%)
A 10 1.2 1.2
0
A 190þ 89 1.5 1.4
A 370þ 70 2.5 1.7
A 565þ 33 5.5 1.8
C 10 1.0 1.0
0
C 190þ 73 1.5 1.1
C 370þ 36 3.0 1.1

Figure 3. Shifting of the normalized asphaltene percent when light cuts are
removed.
Table 3. Asphaltene Onset of Studied Samples Determined by FBRM

Ronset (mLn-C7/gcrude oil)

crude 190þ 37 565þ

oil 0þ
A 2.6 3.9 3.9 3.9
C 0.2 0.2 0.7

Figure 4. Normalized kinetics for samples studied at onset 10%:

(a) crude A and their residues and (b) crude B and the 370þ residue.
Figure 5. CLD study at different times for residue 190þ of crude A.

PSDs in crude oil and residues can be compared at a fixed time, to address
the effect of the composition of the surrounding medium. Figure 6 shows the
results of this analysis for crude A and its residues. At this time, no size shifting
is observed in residues. The amount of particles increases because the
concentration of asphaltenes increases from the crude to the residues. With the
information gath- ered from Figures 4-6, one can conclude that the removal of
light ends slows down the precipitation of asphaltenes but yields particles of
similar size.
Determination of SN. The TURBISCAN stability is cal- culated for all
samples and expressed as SN. Asphaltenes with higher sedimentation rates
(greater SN) are related to more unstable crudes. Panels a and b of Figure 7
show the results for crude A and C, respectively. For crude oils A and C, the
transmittance varies less with time as more light compounds are removed
from the crude, confirming that stability of asphaltenes in residues is increased
with respect to crude oil.
To analyze the contribution of other compounds to sol- vent quality,
Turbiscan experiments were carried out with doped crude oil samples. First, C5-
C7 resins were added in concentrations ranging from 5 to 20%. To assess the
magni- tude of stabilization by resins, equivalent experiments were carried out
 with a diaromatic compound (RMN). Panels a-d of Figure 8 show the evolution
of transmittance with time for all experiments with crudes A and C.
Qualitatively, one can see that the addition of these substances decreases the
variation in transmittance, i.e., increasing the stability of the crude. The SNs are
displayed in Table 4. Larger amounts of the C5-C7 fraction or RMN reduce SN,
indicating that, in both cases, asphaltene stability is increased. Crude A is very
stable (SN lower than 5), and the effect of doping substances is lower. Crude C
is unstable, and the effect is greater, with RMN being a better product than C5-
C7 resins. Nevertheless, the range of variation is very similar for both kinds of
substances.
Coming back to the topic of the role of resins in asphal- tene stability, these
experiments have shown that there is a measurable effect of the C5-C7 fraction
(typically consid- ered inside the resin fraction) on asphaltene stability but the
magnitude of this effect is not as significant as one would expect if it was a
critical factor. This analysis has included both a stable and unstable crude oil.
Moreover, the effect is of a comparable magnitude with respect to the addition
of a diaromatic and also the removal of light ends. Thus, these tests support the
belief that the solvent quality as a whole rules asphaltene behavior.

Figure 8. Results of stability experiments by ASTM D-7061: (a) crude A þ C5-C7

fraction, (b) crude A þ RMN, (c) crude C þ C5-C7 fraction, and (d) crude C þ RMN
Conclusions
With the information gathered from FBRM experiments, one can
conclude that the removal of light ends increases the amount of C7 needed to
reach the onset, slows down the precipitation of asphaltenes, butyields particles
of similar size. Turbiscan results have confirmed that light-end removal from
crude oil leads to the stabilization of asphaltenes. Resins (defined as C5-insoluble
and C7-soluble) and an aromatic compound (RMN) have been doped in the
original crude, to assess their effect on stability. Results have shown that the
C5-C7 fraction increases asphaltene stability to a similar extent as a diaromatic
molecule, such as RMN. All of this evidence indicate that the effect of C5-C7
resins and diaro- matic addition and the removal of light ends have a similar
impact on asphaltene stability, supporting the belief that the
solvent quality as a whole rules asphaltene behavior.

Acknowledgment. Thanks are due to Fernando Dodero Na- valpotro and

Rut Rodriguez Rey for their help with some of the experiments. The authors also
wish to acknowledge the financial support of Repsol.
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