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Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel
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Asphaltene characterization of paraffinic crude oils

Estrella Rogel , Cesar Ovalles, Janie Vien, Michael Moir

Chevron Energy Technology Company, Richmond, CA 94801, USA

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h i g h l i g h t s
 Analyses of solid phases from paraffinic oils revealed the presence of asphaltenes.

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 Asphaltenes with large solubility parameters precipitate together with waxes.

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 Asphaltenes in deposits show larger solubility parameters than ones in the oil.
 Composition of precipitated asphaltenes changes as a function of time.

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a r t i c l e
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i n f o

Article history:
Received 21 December 2015
Received in revised form 2 March 2016
Accepted 10 March 2016
Available online xxxx
Keywords:
Asphaltenes
Paraffins
Waxy crude oils
Deposits
Precipitation
Solubility parameter

a b s t r a c t
Precipitation and deposition of asphaltene and waxes pose a serious challenge to the petroleum industry
since costly remedial actions to maintain operations are required. Even though asphaltenes and waxes
are radically different in chemical nature, they both have low solubility in crude oils, and they frequently
appear together in recovered deposits from wells and pipelines. In this work, we evaluate the solubility
characteristics of the asphaltenes that are naturally associated themselves with the wax crystals present
in several paraffinic crude oils. Filtration was used to separate precipitated waxes from crude oils at room
temperature, and the solubility distributions of asphaltenes associated with the precipitated waxes are
compared with the distributions of the total asphaltenes present in the original crude oils. It was found
that the filtered cakes were enriched in the least soluble asphaltenes as indicated by their larger average
solubility parameters in comparison with the crude oil (21.321.6 MPa0.5 vs. 18.518.6 MPa0.5). These are
the type of asphaltenes likely to be present in deposits together with waxes. Additionally, after filtration,
the filtered crude oil was spiked with pentane asphaltenes and after one week, the precipitated solids
were separated again and analyzed. The results indicated that the precipitated solids were enriched in
higher solubility parameter asphaltenes in comparison to the pentane asphaltenes originally added.
This separation is likely the product of the low solvent power of the maltenes of these crude oils.
Comparison of the precipitated asphaltenes from original and spiked crude oils revealed that those that
precipitated in association to wax crystals had larger solubility (21.321.8 MPa0.5 vs. 20.020.1 MPa0.5)
parameters than those recovered after spiking.
2016 Published by Elsevier Ltd.

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1. Introduction

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The supply of paraffinic crude oils to refineries has grown considerably in the last few years as a consequence of the increasing
production of tight oils [1]. These paraffinic crude oils can bring
significant challenges to downstream operations. Fouling studies
have shown that paraffinic crudes, even containing low amounts
of asphaltenes, had relatively high fouling rates [2,3]. Additionally,
light paraffinic oils are normally blended with heavier crude oils
and therefore, can potentially induce asphaltene precipitation.
Also, wax presence enhances the formation of stable emulsions
during desalting operations [4] and decreases the desalting effi-

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ciency [5]. Further fouling can also be expected in other refinery

units a consequence of the waxasphaltene interactions.
Analyses of sediments recovered from storage tanks indicated
that waxes and asphaltenes often precipitate together forming a
composite material [6]. A similar situation was reported during
the calorimetric analysis of waxy and asphaltenic deposits from
oil wells [7] where paraffins with more than 40 carbon atoms dominate the precipitate composition.
The interaction of waxes and asphaltenes in the crude oil has
been the subject of numerous studies in the last two decades.
These studies have provided significant insight on how asphaltenes
affect the wax appearance temperature [811], rheological
properties [10,11], and wax crystallinity [12]. In addition, waxes
can modify asphaltene behavior [1315]. For instance, they can

Corresponding author.
http://dx.doi.org/10.1016/j.fuel.2016.03.030
0016-2361/ 2016 Published by Elsevier Ltd.

Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
fuel.2016.03.030

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accelerate dissolution of asphaltenes [13] and modify their stability [15].

Asphaltenes and paraffins generate solid complex mixtures
whose formation seems to depend on asphaltene properties and
less on wax composition [13]. Dissolution studies of the composites have shown that the presence of waxes can accelerate the dissolution rate of the asphaltenes. This phenomenon can be
explained by the interaction between peripheral alkyl chains in
asphaltene aggregates and waxes. The interaction increases the
volume of the alkyl layers surrounding asphaltene polyaromatic
cores, and the swelling improves the dissolution of the solids
[16,17].
Calorimetric studies [14,15] showed that the mixing of
n-alkanes with asphaltenes is an exothermic phenomenon. Again,
this is explained by the trapping of n-alkanes in the aliphatic shell
formed by peripheral alkyl chains of asphaltenes. The trapping of
alkanes in the exterior shell of the asphaltenes facilitates the nucleation and deposition of waxes while it can alter the stability of
asphaltenes and induce flocculation. In fact, it is well known that
alkanes precipitate asphaltenes and the amount, and characteristics
of the precipitated asphaltenes depend on the solvent power of the
alkane as well as other variables that include, but are not limited to
alkane/sample ratio, contact time, and temperature [1820].
As shown before, previous studies have led to the conclusion
that asphaltenes and waxes interact synergistically. However,
many of these investigations comprised the use of model systems
where isolated asphaltenes and alkanes/or waxes are blended.
In contrast to these studies where natural conditions are
manipulated, the main goal of the present work is to find out the
asphaltenes characteristics that naturally associated themselves
with the wax crystals present in the crude oil. To this end, filtration
was used to separate precipitated waxes from crude oils at room
temperature and the solubility distributions of asphaltenes associated with the precipitated waxes are compared with the distributions of the total asphaltenes present in the original crude oils.
Additionally, we added asphaltenes to the crude oil after the precipitated solids (original waxes and asphaltenes) were separated
to determine the effect that maltenes and time have on the composition of asphaltene particles.

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2. Experimental section

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2.1. Materials

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Crude oils exhibiting wax crystals at room temperature were

obtained from refinery tanks. These crude oils were associated to
increase fouling in pre-train heat exchangers of the refinery. Pentane asphaltenes were obtained from a heavy crude oil (7.5API)
using the standard test ASTM D 4055 [21]. Methylene chloride,
toluene, chloroform, methanol, and n-heptane HPLC grade solvents
were purchased from Fisher Scientific and used without further
purification.

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2.2. Separation scheme

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Original crude oil samples were filtered using a centrifuge

device with an average pore size of 0.22 lm so that particles could
be recovered and analyzed. Tubes were centrifuged during 1 h at
1500 rpm. The precipitated material and filtered crude oils were
recovered. Pentane asphaltenes were added to the filtered crude
oil, sonicated for several hours and kept into storage for 1 week
in an inert atmosphere. Then, the spiked crude oils were filtered
using the same procedure employed for the original crude oil. A
second set of precipitated materials and filtered spiked crude oil
was recovered. Filter cakes (precipitated materials) and filtrates
were analyzed. Fig. 1 shows the separation scheme.

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2.3. Characterization methods

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Optical microscope observations were made using a Zeiss Axioplan optical microscope with polarized light (Magnification was
200).
Asphaltene concentrations and asphaltene solubility profiles
were determined using on-column filtration techniques [22,23].
In these techniques, a solution of the sample is injected into a column packed with an inert material using n-heptane as the mobile
phase. This solvent induces the precipitation of asphaltenes and, as
a consequence, their retention in the column. To determine the
asphaltene content the mobile phase is switched to a blend
dichloromethane/methanol 90/10 v/v that redissolves the
asphaltenes completely. To determine the asphaltene solubility
profile, the mobile phase is changed gradually from pure
n-heptane to 90/10 methylene chloride/methanol and then to
100% methanol. This procedure gradually re-dissolves the
asphaltenes from the easy to dissolve (low solubility parameter)
to the hard to dissolve (high solubility parameter). In both techniques, asphaltenes are quantified using an Evaporative Light Scattering Detector Alltech ELSD 2000. Rather recently, the method has
been calibrated to produce a distribution of asphaltenes in terms of
their solubility parameters. A description of the calibration is published elsewhere [24].
Carbon, hydrogen, and nitrogen (CHN) analysis was carried out
with a Carlo Erba model 1108 analyzer. Metal and sulfur contents
were determined using a Thermo Intrepid ICP (see Fig. 2).
High-temperature gas chromatography (HTGC) was performed
using a J&W Scientific DB-1HT 30 m  0.320 mm ID  10 lm film
thickness column. A Hewlett Packard/Agilent 6890 with a 7673
autosampler and Flame Ionization Detector (FID) system was used.
Samples were dissolved in HPLC grade CS2 and injected on-column
(1.0 ll). Data were collected and analyzed using an Agilent
EZChrom Chromatographic Data System.

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3. Results and discussion

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3.1. Crude oil characterization

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Table 1 shows the main characteristics of the crude oils used in

the study. All these crude oils exhibit wax crystals at room temperature and contain small amounts of asphaltenes. Fig. 1 shows
examples of microscopic observations for two of the crude oils
under polarized and normal light. In these microphotographs, the
presence of wax crystals is indicated by bright spots under polarized light. Dark particles that appeared under regular light are
identified as asphaltene particles.

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3.2. Precipitated phase of original crude oils

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Table 2 shows the characterization of the filtered cakes

obtained by filtration of the original crude oils. In this table, large
H/C ratios indicate the aliphatic character of the filtered cake that
is expected, as the majority of particles present in the crude oils
were identified as wax crystals. Measurements of the asphaltene
content on the filtered cakes revealed that they contain small
asphaltene amounts ranging from around 4 to 20 wt%. In all the
cases, there is a clear enrichment in the amount of the asphaltenes
in the filtered cake with respect to the original crude oil. However,
even though filtrationcentrifugation provides a direct method to
separate the solid particles from the crude oil, there can be a
significant amount of liquid crude oil entrapped in the filtered
material.
The comparison of the solubility profile of the asphaltenes in
the original crude oils and those found in the filtered cake indicates

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Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
fuel.2016.03.030

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Fig. 1. Scheme of the experiments.

Crude Oil C

Crude Oil D

Fig. 2. Microphotographs of Crude Oils C and D under regular and polarized light.

Table 1
Crude oil characteristics.

Crude
oil

API

A
B
C
D
E

31.4
32.6
32.6
33.5
40.0

Table 2
Characterization of the filtered cakes corresponding to original crude oils.

Asphaltene content
(wt%)

Sulfur
(ppm)

Vanadium
(ppm)

2.78
1.73
1.99
1.69
0.82

7790
785
4390
4440
1970

17.4
1.26
7.91
7.9
a

Nickel
(ppm)
8.25
a

4.03
3.87
1.45

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203

Asphaltene
content (wt%)b

C (wt%)c

H (wt%)d

H/Ce

A
B
C
D
E

4.26
12.76
18.20
7.90
3.60

82.98
81.71
82.19
73.54
84.79

12.56
12.12
10.52
10.86
12.85

1.82
1.78
1.54
1.77
1.82

Values lower than the reporting limit (<1 ppm).

a

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Filtered cakes
crude oila

that this material is enriched in high solubility parameter asphaltenes. Fig. 3 shows two examples of this behavior: Crude Oils B
and C. In these examples, the average solubility parameters of

b
c
d
e

See Section 2 for details.

As determined by using on-column filtration techniques [19,20].
Carbon content as determined by elemental analysis.
Hydrogen content as determined by elemental analysis.
Molar ratio H/C.

Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
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the asphaltenes in the deposits are higher than those in the crude
oils: 21.6 MPa0.5 vs. 18.6 MPa0.5 (Crude Oil B) and 21.3 MPa0.5 vs.
18.5 MPa0.5 (Crude Oil C). This difference can be attributed to preferential precipitation of the least soluble of the asphaltenes. This
data seems to indicate that the asphaltenes more prone to form
aggregates are those with the largest solubility parameters and
therefore, more prone to precipitation as expected. They form particles that are separated together with the wax crystals using filtration/centrifugation. These results are in clear contrast with
previous researchers [25] that reported that asphaltenes in wax
deposits are likely a component of the occluded oil in the deposit.
The results from the present study indicate that the selective precipitation of the least soluble asphaltenes takes place. In fact, this
finding is consistent with reports of asphaltenes deposits being
enriched in highly aromatic components in comparison to heptane
precipitated asphaltenes obtained in the lab [26,27]. The selective
precipitation is to be expected since the least soluble asphaltenes
are those that are likely to be incorporated into the wax and form
deposits. Previously, high aromaticity in asphaltenes has been
linked to low solubility in hydrocarbon solvents and observed in
crude oils with asphaltene precipitation problems [24,28,29]. In
the following section, we will explore the effect that the solvent
power of the analyzed crude oils has on the precipitation of added
asphaltenes.
Fig. 4 shows a comparison of paraffin distribution of Crude Oil C
and its precipitated material. The result shows that the filter cake is
enriched in larger paraffins with respect to the crude oil. It also

contains a significant amount of low molecular weight paraffins

indicating that the deposit contains entrapped paraffins that are
not solids at room temperature.
Filtered crude oils were also analyzed to verify significant
changes in asphaltene content. The results shown in Table 3 indicate that no significant changes were observed in the asphaltene
content of the filtered crude oils with respect to the original ones
except for Crude Oil C. For this crude oil, a decrease of 10% was
observed that is larger than the error of the analytical technique.

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3.3. Spiked crude oils and their precipitated phases

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In order to examine in more detail the effect of the maltene solvent power of crude oils, filtered crude oils obtained after separation of solid particles were spiked by adding approximately 1 wt%

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Fig. 4. Comparison of paraffin distribution for Crude Oil C and its filtered cake.

Table 3
Asphaltene content comparison for filtered crude oil, spiked crude oil and filtered
spiked crude oil.a

Fig. 3. Comparison of asphaltene solubility profiles in crude oil and precipitated

material (filtered cakes) for (a) Crude Oil B and (b) Crude Oil C. Normalized
responses are plotted for comparison purposes.

Label

Filtered crude oil

(wt%)

Spiked crude oil

(wt%)

Filtered spiked crude oil

(wt%)

A
B
C
D
E

2.82
1.76
1.78
1.65
0.75

3.69
2.67
2.71
2.47
1.65

3.55
2.46
2.46
2.27
1.36

As determined using the using on-column filtration techniques [19,20].

Fig. 5. Comparison of asphaltene solubility profiles for Crude Oil B.

Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
fuel.2016.03.030

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of pentane asphaltenes (C: 83.39 wt%, H: 8.07 wt%, Ni: 368 ppm
and V: 1684 ppm). Table 3 shows the increase in asphaltene content of these crude oils as a consequence of this addition. After
the addition, the crude oils were kept in an inert atmosphere for
one week, after that the precipitated material was recovered by filtration/centrifugation. Asphaltenes in the filtered spiked crude oils
as well as in the spiked crude oils were characterized by their solubility profiles. Fig. 5 shows a comparison on the changes on solubility profile of asphaltenes in the crude oils during the different
stages of the experiments for Crude Oil B. In this figure; it can be
seen that the changes are relatively small after spiking and filtration, and they occurred in the whole range of solubility parameters.
Solubility profile analyses of the filtered cakes obtained from
the spiked crude oils were carried out, and the results are shown
in Fig. 6. In this figure, all the filtered cakes except filtered cake A
show enrichment in high solubility parameter asphaltenes with
respect to the original added pentane asphaltenes. Visual inspection of filtered cake A indicated that it contained a significant
amount of crude oil, and, therefore, the solubility profile of its
asphaltenes resembled that of crude oil. Unlike the other cakes,
this filtered cake shows enrichment in low solubility parameter
asphaltenes in comparison to the added pentane asphaltenes indicating that it contains predominantly crude oil.
The solubility profiles shown in Fig. 6 indicate that maltenes
from spiked Crude Oils B to E have a low solvent power that leads

to the separation of the least soluble asphaltenes. The low solvent

power is also the cause of the co-precipitation of asphaltenes with
waxes in the original crude oils as analyzed in the previous section.
This apparent co-precipitation is a phenomenon likely to happen in
many paraffinic crude oils that can lead to high fouling rates as
shown by previous researchers [2,3].

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3.4. Comparison of precipitated phases: original versus spiked crude

oils

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Another interesting aspect is the comparison of the precipitated

asphaltenes observed in the original crude oil with those that precipitated after the spiking of the filtered crude oil. Fig. 7 shows
two examples of these comparisons. In general, it was found that
all the filtered cakes obtained after spiking showed asphaltenes that
were substantially different than those recovered from original
crude oils. In fact, asphaltenes recovered from the original filtered
cakes were characterized by larger solubility parameter asphaltenes than those from the spiked ones. In the case of the examples
shown in Fig. 7, average solubility parameters for the profiles were
20.1 vs. 21.3 MPa0.5 (Crude Oil C) and 20.0 vs. 21.8 MPa0.5 (Crude Oil
B). These differences may be the result of two factors: (1) High solubility parameter molecules are absent in the added pentane
asphaltenes or/and (2) The enrichment with the least soluble
asphaltenes occurs during extended periods of time as it has been

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(a) 8.0E-03

Pentane Asphaltenes

Original Filtered Cake C

7.0E-03

Spiked Filtered Cake C

6.0E-03

Normalized Response

245

Filtered Cake Crude Oil A

5.0E-03
4.0E-03
3.0E-03
2.0E-03

Filtered Cake Crude Oil B

1.0E-03

N
or
m
ali
ze
d

0.0E+00
17

19

21

23

25

Solubility Parameter (MPa 0.5)

Filtered Cake Crude Oil C

(b) 9.0E-03

Normalized Response

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Filtered Cake Crude Oil D

Filtered Cake Crude Oil E

8.0E-03

Original Filtered Cake D

7.0E-03

Spiked Filtered Cake D

6.0E-03
5.0E-03
4.0E-03
3.0E-03
2.0E-03
1.0E-03
0.0E+00
17

15

16

17

18

19

20

21

22

23

24

25

Fig. 6. Asphaltene solubility profile of the filtered cakes obtained from spiked crude
oils. Normalized responses are plotted for comparison purposes.

19

21

23

25

Solubility Parameter (MPa 0.5)

Fig. 7. Asphaltene solubility profile of precipitated phases for original and spiked
crude oils (a) Crude Oil C and (b) Crude Oil D.

Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
fuel.2016.03.030

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8.0E-03

Filtered cakes spiked Crude Oil C

Normalized Response

Aer 3 months
6.0E-03

4.0E-03
3.0E-03

1.0E-03
0.0E+00
17

19

21

23

25

Solubility Parameter (MPa0.5)

Fig. 8. Comparison of asphaltene solubility profiles for spiked Crude Oils B and C
after (a) 1 week and (b) 3 months.

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hypothesizing previously by other authors [26], and therefore,

more time is required to see the effect of this selective precipitation.
In order to shed some light about these two possibilities, spiked
samples were kept in storage, and the precipitated phases were
recovered by filtration.
Fig. 8 shows a comparison of the asphaltene solubility profiles
of the filtered cakes obtained for spiked Crude Oils B and C after
one week and after three months in storage. In both cases, these
figures showed a shift of the profile of the filtered cakes toward larger solubility parameters after three months of storage supporting
the hypothesis of the selective precipitation of the least soluble
asphaltenes occurring during an extended period [26]. The changes
in the distributions show the relative decrease of the more soluble
asphaltenes (low solubility parameters) and the increase of the less
soluble asphaltenes. These changes are compatible with the slow
process of dissolution of the asphaltenes with lower solubility
parameters, while the asphaltenes with larger solubility parameters remain and become prevalent in the aggregates/particles. This
finding is also consistent with the results showing that deposits
from upstream as well as downstream are enriched in the least soluble asphaltenes present in the crude oil [30,31].

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4. Conclusions

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The analysis of several paraffinic crude oils revealed the presence of asphaltenes in the precipitated phase separated by filtrationcentrifugation.

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Acknowledgments

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The authors are grateful to Kaustav Chaudhuri for the

microphotographs, Chevron ETC is acknowledged for providing
funding and the permission to publish this paper.

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5.0E-03

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Aer 1 week

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These asphaltenes are composed of the least soluble asphaltenes present in the crude oil as indicated by larger average solubility
parameters. These are the asphaltenes likely to be present in
deposits together with the waxes.
Analysis of filtered cakes produced by the spiking of crude oils
with pentane asphaltenes indicates that the separation of the least
soluble asphaltenes is likely the product of a low solvent power of
the maltenes.
Comparison of the precipitated asphaltenes from original and
spiked crude oils revealed that those that precipitated in association to wax crystals had larger solubility parameters than those
recovered after spiking.
Asphaltene recovered after spiking of the crude oils changed as
the spiked crude oils aged: they get enriched in higher solubility
parameter species supporting the hypothesis of selective precipitation of the least soluble asphaltenes occurring during an extended
period.

Please cite this article in press as: Rogel E et al. Asphaltene characterization of paraffinic crude oils. Fuel (2016), http://dx.doi.org/10.1016/j.
fuel.2016.03.030

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