INFLUENCE OF HYDROCARBON

DISTRIBUTION IN CRUDE OIL

A N D R E S I D U E S O N A S P H A LT E N E
STABILIT Y
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.
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
INTRODUCTION
The asphaltene fraction is traditionally defined as a solubi- lity class. This definition, apart from creating
significant confusion in the literature, 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 oils rather than with heavy aromatic crudes with high asphaltene concentrations. 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. 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. Several thermodynamic models have been derived from this kind of interaction between
asphal- tenes and resins.Even if significant concerns 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 solvents and also inside crude oil.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
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 CRUDE OIL °API SOURCE CLASSIFICATION
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% A 21 South Naphthenic
pure) was used as received. R-Methyl-naphthalene (tagged as RMN in America
this work, 97%) was used as received. All of the reagents have been
supplied by Scharlab S.L. C 34 South Paraffinic
Asphaltene Separation. The amount of asphaltenes of crude oils and America
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 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.
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, the CLDs were trans- formed into particle
size distributions (PSDs)
 Figure 1 Figure 2
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
 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.
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.

Figure 3
 Asphaltene Aggregation Kinetics by FBRM.
A kinetic study was carried out to determine the
aggregate behavior of asphaltene. The 10% excess
heptane criterion was modified for an onset value
below 1 mL / g, because 10% is not a significant
increase if the onset is around 0.2 mL / g. In this
case, an addition of 0.1 mL / g was made to achieve
the desired excess n-heptane, ie 10% excess. The
results for both crude oil are shown in panels a
and b in Figure 4. The number of counts in the
kinetic study was normalized for all samples with
maximum values measured in the intervals shown
in the figure. For crude oil A, it is observed that
kinetics is slower when the end of the light is
removed, leading to a greater time until the final
particle size is reached; Slow kinetic growth shows
that bitumen is more stable in residue than in Figure 4
crude oil. Crude C doesn't show any trends.
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.
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