Article

pubs.acs.org/EF

Asphaltene Adsorption from Hydroconverted Bottoms

Jeramie J. Adams,*, John F. Schabron, Joseph F. Rovani, Jr., Frans G. A. van den Berg,
and Carl Mesters

Western Research Institute, 3474 North Third Street, Laramie, Wyoming 82072, United States
Shell Global Solutions International B. V., Grasweg 31, 1031 HW Amsterdam, The Netherlands

Shell International Exploration & Production, Inc., 3333 Highway 6 South, Houston, Texas 77082, United States

ABSTRACT: The adsorption of asphaltenes from hydroconverted bottoms (HCB) was evaluated using the Asphaltene
Determinator to quantify the amount of asphaltenes removed, track the changes in the asphaltene solubility prole, and gauge the
selectivity of removing the most aromatic asphaltenes as judged by the 500 nm Coke Index. Adsorption onto a variety of silica gel
sorbents was investigated to determine the importance of surface area relative to pore diameter and pore volume. The adsorption
behavior of HCB was compared with that of unprocessed bitumen from the Peace River area (PRFR), which contains
signicantly larger asphaltenes that were more sensitive to sorbent pore properties. Additionally, the optimum adsorption
temperature for the unprocessed PRFR asphaltenes was much higher than that for HCB asphaltenes. Adsorption of asphaltenes
from HCB improved the quality of the oil by signicantly reducing its viscosity, increasing the H/C ratio, decreasing the nitrogen
and total basic nitrogen, increasing the P value, removing precoke-type asphaltenes, and reducing Ni and V.

INTRODUCTION
In addition to asphaltene precipitation, asphaltene adsorption is
a phenomenon that is often undesirable since it can lead to
unfavorable wetting of reservoir surfaces, which can lead to
clogging and reduced production.13 In upstream applications,
asphaltene adsorption can lead to ow assurance issues,
including pipeline clogging, leading to increased pumping
costs, energy inputs, and greenhouse gas emissions in addition
to costly shutdowns.4,5 Similarly, asphaltenes adsorb to create
deposits on other transportation equipment. If asphaltenes
adsorb onto water droplets, then problematic stable emulsions
can form.610 Asphaltene adsorption is also thought to be an
initiation step leading to fouling of heat transfer surfaces such as
heat exchangers and furnaces.11,12 Furthermore, asphaltene
adsorption can irreversibly poison upgrading catalysts.1315
Asphaltenes are dened by their solubility: they are oil
components that are insoluble in alkanes but soluble in
aromatic solvents. Many dierent types of molecules can report
to the asphaltenes fraction, such as waxes, phorphyrins
containing Ni and V, and other metal-chelating structures,
but it is generally accepted that the bulk of the asphaltene
molecules consist of surface-active polyaromatic hydrocarbons
containing a few percent of N, S, and O in a variety of
functional groups at variable locations within the molecules.
The peripheries of these polyaromatic molecules are decorated
with variations of naphthenic cycles and aliphatic side chains.
These large (average around 700 Da), complex surface-active
molecules strongly self-associate in solution to form nanoaggregates at low concentration (<50 to 100 mg/L), and with
increasing concentration these nanoaggregates usually further
associate into clusters of nanoaggregates.4,1618 The strong
intermolecular forces that drive asphaltene self-association to
form nanoaggregates also promote adsorption onto other
surfaces and at interfaces. These forces include -stacking,19
dipoledipole, acidbase, hydrogen-bonding, hydrophobic 2015 American Chemical Society

pocket, and electrostatic interactions. These forces work

together to align the asphaltene molecules in a local
thermodynamic minimum energy by self-assembly. The
resulting nanoaggregate structures depend upon the geometry,
sterics, and composition of the asphaltene molecules and their
concentration, interactions with other molecules, temperature,
and pressure.20,21
One of the most popular ways to mitigate asphaltene-related
problems is to selectively remove the asphaltenes; this strategy
is often called carbon rejection. This is commonly practiced in
the industry by solvent deasphalting processes or by coking.14
Another such method for selectively reducing the amount of
asphaltenes in petroleum is to intentionally adsorb them onto a
high-surface-activity sorbent. A signicant amount of previous
work has been carried out to understand and optimize
asphaltene adsorption behavior, and a summary can be found
in a recent review article.21 In general, asphaltene adsorption is
enhanced by sorbents of smaller particle sizes relative to those
of larger particles. Adsorption is also enhanced by sorbents with
high pore volumes and large pore diameters that allow ecient
transport of oil and asphaltenes into the pore structure without
becoming signicantly hampered by pore plugging.22,23 More
aromatic asphaltenes are more easily removed by adsorption,
and N and O heteroatoms are usually signicantly reduced
upon adsorption, while S is less aected. Other improvements
in asphaltene adsorption can be gained by tuning the chemistry
of the sorbent surface.
Hydroconversion is a common method to upgrade heavy oil
fractions, bitumen, and residua with catalysts at high temperatures under high pressures of hydrogen to produce additional
higher-value fuel fractions. The process breaks larger molecules
Received: September 15, 2015
Revised: November 13, 2015
Published: December 3, 2015
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approximately 7 in. (18 cm) in length with an outer diameter of 1 in.

(2.5 cm), an inner diameter of 0.75 in. (1.9 cm), and an internal
volume of about 52 mL.
Sorbents were activated and dried in a vacuum oven at 100 C
under full dynamic vacuum for at least 16 h. Dried sorbents were
cooled to ambient temperature under vacuum, and the vacuum oven
was backlled with argon prior to loading of the sorbent into the
reactors. Sorbents were measured by volume using a graduated
cylinder with repeated tapping of the cylinder to maximize packing of
the sorbent. For consistency, repeat experiments using the same
sorbent at the same amount were conducted using the same weight of
sorbent.
In most cases the reactor tubes were charged with 25 0.05 g of
HCB or PRFR and purged with argon. For each set of experiments,
one reactor was immediately capped after the argon purge and used as
a reaction control to monitor heating eects of the oil inside the
stainless steel reactors in the absence of sorbent. AD analysis of each
respective reaction control, per set of experiments, was used as a
baseline for each sorbent treatment. The reactors were run in batches
of four or less, and unless noted otherwise, they contained a volume of
sorbent (25 mL) numerically equal to the weight of oil (25 g). For
sorbent treatment experiments, after the reactors were loaded with oil
and purged with argon, they were charged with dried argon-purged
sorbent and then quickly capped. The reactors were placed in a 150
300 C uidized sand bath and agitated using a custom rack attached
to a motor that gently rocked one end of the reactors up and down
through 1.5 in. equal positive and negative deections at a rate of 41
cycles/min. After the desired treatment time, the reactors were
removed from the sand bath and placed in front of a fan set at high
speed to facilitate cooling (the reactors reached ambient temperature
in less than 45 min when treated at 300 C). About 1 g of oil was
sampled from each reactor and analyzed using the AD. The treated oils
were collected from the sorbents by ltering the reactor contents
through 60 or 100 mesh screen using a heat lamp to warm the
reactors. In some cases the reactors and ltering setup were placed in a
vacuum oven at 7080 C that was purged with argon and held under
a positive pressure of argon. The collected treated oils were
homogenized by stirring prior to AD analysis. For each set of samples
submitted for AD analysis, a 1 g sample of the original HCB or PRFR
was used as a quality control check.
Desorption Experiments. Spent Grace silica containing adsorbed
asphaltenes was ltered from the treated oil as described above. The
ltered Grace silica (25 mL) was taken up in toluene (100 mL) and
gently agitated for 30 min. The toluene solution was carefully decanted
from the spent Grace silica, and fresh toluene was added. The
procedure was repeated about eight times until the toluene rinse
became transparent with a light yellow coloration. Soxhlet extraction
of the toluene-rinsed spent Grace silica was carried out using coarse or
medium glass-fritted Soxhlet thimbles in a Soxhlet apparatus that held
about 80 mL of solvent before draining. Up to 35 mL of spent sorbent
was loaded into the Soxhlet thimble. A 250 mL round-bottom ask
containing about 100 mL of solvent or solvent mixture was attached to
the Soxhlet apparatus. The top of the Soxhlet apparatus was tted with
a water-cooled condenser. All of the joints were greased with hightemperature uorinated Krytox grease. The entire apparatus was
purged with argon for at least 15 min, after which heat was applied to
the 250 mL round-bottom ask and the liquid was brought to reux,
causing the solvent to collect in the Soxhlet thimble. Argon was kept
owing during the entire extraction. The extractions were stopped
when the extracts became colorless or nearly colorless. In most cases
this was completed in about 68 h. Upon completion, the heating
mantle was removed from the round-bottom ask, and the apparatus
was allowed to cool to ambient temperature before the argon purge
was switched o.
For regenerated Grace silica experiments, the toluene-rinsed spent
Grace silica was extracted with (90:10 v/v) N-methyl-2-pyrrolidone
(NMP)/n-butylamine. While still in the Soxhlet thimble, the extracted
Grace silica was placed on a vacuum ask and rinsed four times with
methylene chloride (100 mL) using suction. After the majority of the
methylene chloride was removed from the thimble, the vacuum was

into smaller molecules by cleaving carboncarbon bonds while

also hydrogenating some small aromatics and polyaromatics.
Addition of hydrogen serves to hydrogenate radical species and
olens and to minimize coke formation and condensation
reactions of cracked species to form larger aromatic
species.14,24,25 Hydroconverted bottoms (HCB) are generally
a low-value renery product that may have potential as a
valuable feedstock if treated properly. One of the challenges of
using HCB as a feedstock is that they contain very polar
asphaltenic components, moderately high carbon residue, and
signicant amounts of Ni and V.26 One way to improve the
processability of the HCB is to remove the asphaltene-type
components by adsorption.

EXPERIMENTAL SECTION

Feedstocks. The oils were provided by Shell and used as received.

HCB was obtained from a commercial LC-ner. Peace River bitumen
(PRFR) is an unprocessed bitumen extracted from Canadian oil sands.
Materials. The silica gel sorbents Davisil grade 636, Davisil grade
646, and Merck grade 10181 were purchased from Sigma-Aldrich, and
all of the other sorbents were provided by Shell. Select textural
properties of all of the silica-based sorbents are given in Table 1.
Textural properties of the Sigma-Aldrich silica gel samples were
obtained from Sigma-Aldrich. Textural properties of Grace silica gel,
silica extrudates, silicaalumina extrudates, and alumina extrudates
were measured by both BrunauerEmmettTeller (BET) analysis and
mercury porosity. Reported pore diameters and pore volumes were
obtained from the mercury porosity data. Silicaalumina extrudates
had a surface area of 414 m2/g, a pore volume of 0.78 mL/g, and a
pore diameter of 73 nm. Alumina extrudates had a surface area of 225
m2/g, a pore volume of 0.77 mL/g, and a pore diameter of 122 nm. All
of the solvents and inert gases were reagent or technical grade,
respectively. Solvents and inert gases were purchased from commercial
sources and used as received. Crushed sorbent was prepared by placing
the sorbent in a cloth towel and crushing it with a rubber mallet. The
resulting material was sieved over 14 and 35 mesh or 35 and 60 mesh
screens.
Analytical Asphaltene Determinator Separation. The oncolumn asphaltene precipitation and redissolutionAsphaltene
Determinator (AD)experiments were conducted on custom
ground-PTFE-packed high-performance liquid chromatography
(HPLC) columns as described in detail by Schabron, Rovani, and
Sanderson.27 The analytical setup used a Waters 717plus auto sampler,
a Waters 60F pump with a model 600 controller, a Waters 2489 UV/
vis absorbance detector, and a Waters 2424 evaporative light scattering
detector (ELSD). Solutions of the sample oils were prepared as 10%
(w/v) solutions in chlorobenzene, and solutions of asphaltenes were
prepared as 2% (w/v) solutions. The solutions were ltered through
0.45 m syringe lters into autosampler vials. Portions of 20 L were
injected for the analytical-scale AD separation. All of the separation
proles were electronically blank-subtracted prior to peak integration.
Analysis of the asphaltene content and asphaltene solubility prole
by the AD provided rapid information on the amount of asphaltenes
removed upon adsorption and the selectivity of the asphaltenes
removed. The material detected by the ELSD, which was soluble after
the chlorobenzene solution was precipitated with excess heptane onto
ground Teon, was the maltene content, and this value subtracted
from 100 gave the AD asphaltene content. In addition to quick
turnaround times and high repeatability compared with gravimetric
asphaltene separations, the method requires 1 g of sample, allowing
for smaller-scale evaluations while using signicantly less solvent than
traditional methods.
Adsorption Experiments. Reactor tubes were constructed using
316 stainless steel tubing with 316 stainless steel Swagelok VCR end
ttings. Each reactor tube consisted of two threaded nut assemblies
sealed with metal VCR gaskets. The design enabled convenient lling
of oils, removal of oils and sorbents, and cleaning. TIG welding was
used to attach the components to the tubing. The reactors were
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The circulating temperature bath was set at 50 or 60 C, and the

titrant pump speed was set to 0.10 mL/min. The vessel containing the
oil dissolved in 1-methylnaphthalene was tted with a Teon-coated
stir bar and stirred vigorously at the same rate during the entire
experiment. This vessel was allowed to stir for 5 min to allow for
temperature equilibration followed by another 5 min with the solution
owing through the titrimeter tubing and the 740 nm absorbance cell.
After a total equilibrium time of 10 min, the titration was started. The
maximum in the transmittance was recorded as the onset of
occulation, which was used to calculate the oil component solubility
parameters and the P value.
Thermogravimetric Analysis. Thermogravimetric analysis
(TGA) tests were conducted using a TA Instruments Q5000
thermogravimetric analyzer (TA Instruments, New Castle, DE). No
more than 20 mg of material was placed in a platinum TGA pan and
heated at 10 C/min under nitrogen to 600 C. The sweep gas was
switched to air, and the samples were held at 600 C for 15 min.

increased, and the Grace silica was further dried by sucking air through
the thimble. Regenerated Grace silica was nally dried in a vacuum
oven at 170 C for 48 h prior to reuse.
Total Acid Number and Total Base Number Titrations.
Potentiometric titrations for total acid number (TAN) were performed
according to ASTM D-664, and total base number (TBN) titrations
were performed using ASTM D-4739. Titrations were carried out
using a Metrohm 848 Titrino Plus titrator tted with a model 859
compact sample changer.
Elemental CHNOS and Ni and V Analyses. Elemental analyses
were performed by Human Laboratories (Golden, CO). For Ni and
V analysis, the oils were digested by a proprietary method developed at
the Western Research Institute (WRI) that involves heating of about
0.5 g of oil and concentrated sulfuric on a hot plate to dryness
followed by ashing in a mue furnace at 520 C. The ash was
dissolved in aqueous nitric acid, which provided the digested solution.
The nitric acid solutions were analyzed by Human Laboratories by
inductively coupled plasma atomic emission spectroscopy capable of
analyzing 30 elements. Two blanks and a QC sample of a wellcharacterized Unitar round-robin Athabasca bitumen with known
metals content were digested and analyzed to provide limits of
detection and quantication and as a quality control check.
Gravimetric Isolation of Asphaltenes. The oil was weighed and
mixed with an excess of heptane (40:1 v/w) with magnetic stirring.
The mixture was heated to 70 C, allowed to cool to ambient
temperature, and stirred overnight to allow for full precipitation of
asphaltenes. The mixture was allowed to sit undisturbed for 30 min
and was then vacuum-ltered using a 10 m medium-frit sintered glass
lter with repeated rinsing with heptane (usually requiring at least
another 40 volumes of heptane) until the ltrate was colorless. The
obtained solid is termed 10 m asphaltenes. The ltrate was subjected
to a second ltration using a 0.45 m polytetrauoroethylene lter,
and the obtained solid was rinsed with heptane as was done for the 10
m asphaltenes. This material is termed 0.45 m asphaltenes. In this
study, only 10 m asphaltenes were analyzed. Any residual solvent in
the asphaltenes was removed in a vacuum oven under full dynamic
vacuum at 110 C for at least 1 h.
Viscosity Measurements. For this work, the viscosities of the
HCB samples were measured using a Cambridge Viscosity VISCOpro
2000 small-sample viscometer. The unit is an oscillating piston
viscometer that can measure viscosities from 0.25 to 10 000 kPa s with
as little as 2 mL of sample. A liquid cooling/heating jacket and a silicon
oil temperature bath enable viscosity measurements to be performed at
temperatures ranging from 40 to 110 C. Operation of the unit is
described in ASTM D7483. Measurements on treated HCB were
conducted at 60 C with a calibrated piston for the appropriate
viscosity range.
Size-Exclusion Chromatography. Size-exclusion chromatography (SEC) data were collected by preparing 1.0%, and 0.1% (w/v)
solutions in tetrahydrofuran (THF) or toluene. The solutions were
ltered through a 0.45 m syringe lter, and 40 L aliquots were
injected onto an HPLC system with a Phenogel 5 m particle size
linear (2) mixed-bed column thermostated at 30 C and a dierential
refractive index (RI) detector. Toluene or THF was used as the mobile
phase, which was added at a rate of 1.0 mL/min. Waters EmPower
software calculated the molecular weights (MWs) of the resulting
chromatograms using polystyrene standards with MWs of 70 600,
10 900, 3000, 1920, and 266 Da.
Automated Flocculation Titration. Automated occulation
titrimeter (AFT) experiments were performed by modifying the
ASTM D6703 method using a Koehler K47100 AFT (developed by
WRI and licensed to Koehler Instruments, Long Island, NY). The
method was modied to be run similar to ASTM D7060. Three to four
dierent sample solutions of HCB or treated HCB were dissolved in 1methylnaphthalene at ambient temperature and allowed to sit for at
least 24 h until all of the oil was dissolved. The sample solutions
typically contained 0.5, 1.0, 1.5, and 2.0 g of HCB in 3 mL of 1methylnaphthalene, and the solutions were titrated with cetane. The P
values were calculated as specied in ASTM D6703.

RESULTS AND DISCUSSION

Dierence in Optimum Asphaltene Adsorption
Temperature for HCB and PRFR. To optimize the
temperature of the adsorption process, experiments were
conducted at various temperatures for both HCB and PRFR
using Grace silica gel at a 1:1 (w/v) ratio of oil to sorbent.
Adsorption experiments were conducted for 4 h at 50 C
increments between 150 and 300 C. AD analyses of the
treated oils showed that the optimum temperature of
adsorption for HCB was around 200250 C, whereas
adsorption was more ecient for PRFR at 300 C (Figure
1). The higher temperature of adsorption for PRFR may be

Figure 1. AD results showing the amounts of asphaltenes removed

after heating mixtures of 25 g of oil and 25 mL of Grace silica gel.

necessary since it contains virgin unpyrolyzed asphaltenes that

may require more energy to dissociate aggregated asphaltenic
structures. A total of 10 repeat adsorption experiments using
Grace silica gel (25 mL) and HCB (25 g) were conducted with
a contact time of 4 h at 200 C. AD analysis of the treated HCB
from these experiments showed there to be 2% absolute error
in the amount of asphaltenes removed. Similarly, tests with four
replicate experiments using PRFR and Grace silica gel at 300
C for 4 h also showed there to be 2% absolute error in the
amount of asphaltenes removed.
To determine the optimum contact time for maximum
adsorption of HCB asphaltenes onto Grace silica gel, a series of
adsorption experiments were carried out with contact times of
0.5, 1, 2, 4, 6, 8, 12, and 16 h at 200 C. The initial set of
experiments showed that adsorption peaked at about 6 h of
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contact time and then dropped o. The adsorption capacity at
6 h was only slightly increased (0.5%) relative to those in
experiments conducted at 4 and 8 h, and therefore, additional
adsorption experiments were conducted for 4 h for
convenience. Figure 2 shows the amounts of AD asphaltenes

Figure 3. Amounts of AD asphaltenes removed at 200 C with a

contact time of 4 h for varying oil to sorbent (HCB:Grace silica) ratios
of 40:10, 35:15, 30:20, 25:25, and 20:30 (w/v).

Figure 2. AD results showing the amounts of asphaltenes removed

after adsorption onto Grace silica gel at 200 C at various time
intervals.

removed in the time-dependent experiments using HCB and

Grace silica gel. A repeat set of experiments from 1 to 8 h gave
similar results showing a maximum in the asphaltene
adsorption at around 46 h.
Determining the adsorption capacity is crucial since this
determines how much oil can be treated by a given quantity of
sorbent, which in turn dictates the size of the adsorber unit.
Capacity studies for Grace silica were carried out by varying the
oil to sorbent (HCB:Grace silica) ratio from 40:10 (w/v) to
35:15, 30:20, 25:25, and 20:30 (w/v). A linear correlation (R2 =
0.9685) between the sorbent volume and the amount of
asphaltenes removed (2080% asphaltenes removed) was
observed, which demonstrates that the adsorption capacity of
the Grace silica was passivated by asphaltenes at all of the ratios
surveyed. HCB:Grace silica ratios greater than 20:30 (w/v)
were not practical because the treated oil remained entrained
within the pore volume of the Grace silica and could not be
ltered from the sorbent. Figure 3 shows the amounts of
asphaltenes removed at dierent HCB:Grace silica ratios.
A similar capacity study was carried out using silicaalumina
extrudates that were crushed and sieved between 14 and 35
mesh. A linear correlation between the amount of asphaltenes
removed and the volume of sorbent similar to that with Grace
silica was found (Figure 4). The slightly higher adsorption
capacity for the silicaalumina is likely a function of the
increased surface area since the pore volume and diameter of
the sorbent are similar to those of Grace silica (5094 m2 of
silicaalumina was added to the reactors vs 3468 m2 for Grace
silica).
Dierences in Optimum Pore Size for HCB and PRFR
Using Silica. Several dierent silica samples were obtained to
investigate the relationships between adsorption capacity,
surface area, pore diameter, and pore volume. Merck grade
10181 silica gel and Davisil grades 636 and 646 silica gel (from
here on denoted as 10181, 636, and 646 silica gel, respectively)
were purchased from Sigma-Aldrich and are similar in particle
size to the Grace silica. The pore diameters of the dierent

Figure 4. Amounts of AD asphaltenes removed at 200 C with a

contact time of 4 h for varying oil to sorbent (HCB:SilicaAlumina)
ratios of 40:10, 35:15, 30:20, 25:25, and 20:30 (w/v).

silica samples increase in the following order: 10181 < 636 <
Grace < 646. The pore volumes followed the same trend, while
the surface areas were in the reverse order. Another set of silica
sorbents was provided by Shell. These were signicantly larger
extrudates that were calcined from 500 to 1000 C. The
calcining process increased the pore diameter while simultaneously decreasing the pore volume and surface area (surface
silanol, SiOH, groups are also reduced). The structural
properties of the dierent silica samples are given in Table 1.
By using sorbents with dierent textural properties it was
determined that the adsorption of HCB and PRFR are more
aected by two dierent physical properties. The dierences
were observed by plotting the percent change in AD
asphaltenes against the pore diameter (), pore volume
(mL/g), and surface area of the added silica sorbent (m2/25
mL) for adsorption with HCB (Figure 5) and PRFR (Figure 7).
For HCB asphaltenes, adsorption was found to correlate with
increasing surface area for all of the silica sorbents except
10181. The relatively smaller pore volume and pore diameter of
10181 were presumably too restricting to allow ecient
transport of asphaltenes into the inner structure of the silica
gel, causing it to fall outside the trend. The amount adsorbed
dropped considerably between 636 (60 diameter)which
had the highest adsorbed amountand 10181 (40
diameter). A complex relationship between the amount
adsorbed and pore volume of the sorbent was observed,
which is discussed further in the next paragraph. It is clear that
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Table 1. Selected Structural Properties for the Silica Gel Sorbents 10181, 636, Grace silica, and 646 and Silica Extrudates
Calcined at 500, 600, 700, 800, 900, and 1000 C and Percent Changes in AD Asphaltenes for HCB and PRFR Relative to
Control Experimentsa
% change in
asphaltenes

Merck grade 10181

Davisil grade 636
Grace silica
Davisil grade 646
silica 500 C
silica 600 C
silica 700 C
silica 800 C
silica 900 C
silica 1000 C

pore diameter
()

pore volume
(mL/g)

surface area
(m2/g)

mass of silica per 25 mL

(g)

density
(g/mL)

m2/25 mL

HCB

PRFR

40
60
86
150
205
209
212
229
287
330

0.68
0.75
1.06
1.15
1.32
1.30
1.28
1.19
1.08
0.65

675
480
365
300
346
337
326
268
169
84

13.49
12.39
9.55
9.34
7.92
8.03
8.17
8.84
9.65
13.17

0.540
0.495
0.382
0.374
0.317
0.321
0.327
0.354
0.386
0.527

9108
5946
3486
2801
2741
2706
2665
2371
1626
1106

31.9
58.6
48.7
46.1
28.1
28.4
27.6
25.2
23.4
15.2

22.1
27.6
30.6
31.9
11.1
9.4
12.5
17.2
22.1
15.7

Adsorption experiments were conducted for 4 h using 1:1 (w/v) oil to silica. PRFR adsorption experiments were carried out at 300 C, while HCB
adsorption experiments were carried out at 200 C.

adsorption of HCB asphaltenes is strongly related to the

available surface area until the pore diameter becomes too
constricting to allow ecient diusion of asphaltenes. The
limited adsorption at smaller pore diameters may also be
compounded by considerable pore plugging at or near, the
entrance of the pore. The other factor not taken into
consideration is the structuring, or morphology, of the pore
volume. In light of these results, ecient adsorption of HCB
asphaltenes onto silica gel becomes inhibited by pore diameters
below 60 .
The complex relationship between the pore volume and the
amount of asphaltenes adsorbed has to do with the fact that as
the pore diameter increases the surface area decreases for all of
the silica samples, whereas the changes in the pore volume for
the silica gel samples and the calcined silica extrudates move in
opposite directions. For the set of silica gel sorbents (10181,
646, 636, and Grace silica), as the pore diameter decreases (or
the surface area increases), the pore volume decreases.
However, for the set of calcined silica extrudates, as the pore
diameter decreases (or the surface area increases), the pore
diameter increases (Figure 6). Additional disparities between
the adsorption data for the silica gel samples and the calcined
silica extrudates may be related to the larger size of the calcined
silica extrudates. In short, for optimal HCB asphaltene
adsorption, a pore diameter of around 60 or larger is
necessary, and increasing the pore volume and surface area
increases the adsorption. All of these results are consistent with
literature reports.21
PRFR asphaltenes, on the other hand, did not give the same
expected correlation with the surface area over the whole series
of silica sorbents. For the smaller-pore set of silica gel sorbents
(10181, 646, 636, and Grace) there was a very strong negative
linear correlation between the surface area and the amount of
asphaltenes adsorbed (R2 = 0.9941), whereas for the calcined
silica extrudates there was no linear dependence (Figure 7 top).
For the extrudates, adsorption did generally increase with
decreasing surface area, increasing pore diameter, and
increasing calcination temperature, except for the 1000 C
calcined silica. In general, as long as asphaltenes can diuse into
the sorbent, adsorption is expected to increase with increasing
surface area. The fact that adsorption from PRFR generally

decreases with increased surface area can be explained by the

dierent pore diameter requirements for PRFR asphaltenes.
Focusing on the results for the treated PRFR from the 10181,
646, 636, and Grace silica gel series of sorbents makes it clear
that PRFR asphaltene adsorption has a strong dependence on
the pore diameter: as the pore diameter increases, the
adsorption increases. For the calcined silica extrudates, as the
pore diameter increased, the adsorption also increased, except
for the 1000 C calcined silica. The signicantly reduced
amount of asphaltenes adsorbed using the 1000 C calcined
silica is likely related to its dramatically reduced surface area,
pore volume, and silanol surface coverage. The dierence in the
magnitudes of adsorption by the 10181, 646, 636, and Grace
silica gel set of sorbents and the calcined silica extrudates is
likely due to the signicant dierence in the size of the sorbent
particles (see later). The calcined silica extrudate particles are
signicantly larger, and since pore plugging occurs, this reduces
the ability of PRFR asphaltenes to access more of the internal
surface area of the sorbents. For PRFR asphaltenes, the
adsorption is limited by access to the pore surface area provided
by the pore diameter. For the silica sorbents surveyed here,
access of PRFR into the porous structure is signicantly more
important than the amount of surface area. Ideally, more
selective adsorption of PRFR asphaltenes would require a
sorbent that has a large pore diameter, pore volume, and
surface area. The stronger pore diameter dependence for
asphaltene adsorption from PFRF relative to HCB is in
agreement with the SEC data, which showed that PRFR
asphaltenes are signicantly larger than HCB asphaltenes (see
later). Figure 7 shows the relationships between the amount of
PRFR asphaltenes adsorbed and the sorbent textural properties
of surface area, pore volume, and pore diameter.
It is known that pyrolysis, or cracking, causes native
asphaltene and resin molecules to become smaller as a result
of cleavage of aliphatic side chains and naphthenic
cyclics.23,28,29 In order to show that the asphaltenes in HCB
are smaller than those in unprocessed PRFR asphaltenes, SEC
was performed on heptane asphaltenes from HCB and PRFR in
toluene and THF at very low concentrations to minimize selfassociation eects.28 Solutions with concentrations of 1% and
0.1% in toluene and 1% in THF all showed that HCB eluted at
signicantly longer times than PRFR asphaltenes, indicating
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Figure 6. Relationship between the pore diameter and pore volume for
the silica sorbents. The red squares are for the calcined silica
extrudates, and the blue diamonds are for the 10181, 646, 636, and
Grace silica gel sorbents.

higher molecular weight of the PRFR asphaltenes relative to the

average value of 700750 Da often reported in the literature
implies that the PRFR asphaltenes are likely associated species.
Similar conclusions were obtained by TGA conducted on
HCB and PRFR, which showed that HCB contains more
volatile material with a narrower boiling point distribution than
PRFR. The data also show that HCB has signicantly less
pyrolysis material and also much less higher-MW-range
material than PRFR (Figure 9). The signicantly reduced
amount of pyrolysis material in HCB (shoulder around 500 C)
conrms that HCB contains very few aliphatic side chains and
naphthenic cyclics attached to aromatic structures.
The fact that PRFR asphaltenes are signicantly larger than
HCB asphaltenes and self-associate to a greater degree explains
why optimal PRFR adsorption occurs at higher temperature
(which helps to break up aggregation) and why adsorption is
signicantly more sensitive to the pore diameter and particle
size (which aect diusion into the sorbent structure). Others
have reported a similar increase in asphaltene adsorption for
visbroken asphaltenes compared with original asphaltenes.3033
In regard to particle size and pore plugging, as the particle
size of the sorbent increases it is less likely that the surface area
contained within the internal pore volume can be accessed
since asphaltenes adsorbed onto and around the pore openings
restrict and eventually block further diusion of asphaltenes
deep into the sorbent. In regard to particle size, the silica gel
sorbents 10181, 646, 636, and Grace silica consist of small,
irregular particles ranging from about 14 mesh to 70 mesh. The
silica extrudates, on the other hand, are much larger cylinders
that are approximately 2.5 mm in diameter and range from 3 to
8 mm in length. Pore plugging near the outer edges of the
larger calcined silica extrudates inhibits asphaltenes from
reaching all of the internal surface area contained within the
pore volume. This is why the silica extrudates adsorb less
asphaltenes overall than the smaller-particle silica, especially for
the larger PRFR asphaltenes (Figure 7). Likewise, the
discrepancy between the adsorption capacities of the silica gel
samples and the silica extrudates (Figure 5) may be less obvious
for HCB because the asphaltenes are much smaller than PRFR
asphaltenes.
Eect of Particle Size. A more comprehensive set of
diusion and pore plugging experiments were conducted using
the same weight (surface area) of alumina extrudates in three
dierent sizes: whole (2 mm diameter 38 mm long), 1435

Figure 5. Percent change in AD asphaltenes after adsorption with

HCB plotted versus (top) the surface area of 25 mL of added sorbent,
(middle) the pore volume, and (bottom) the pore diameter of various
silica sorbents. The red squares are for the calcined silica extrudates,
and the blue diamonds are for the 10181, 646, 636, and Grace silica gel
sorbents. The results for the 10181 silica gel treatment were omitted
from the linear regressions.

longer residence times and thus smaller molecules. Figure 8

shows the 500 nm optical absorbance detector data for HCB
and PRFR asphaltenes eluted with toluene. The values obtained
for the molecular weights of HCB asphaltenes were smaller
than expected, so the experiments were repeated using THF as
the solvent. THF is a stronger chromatographic solvent that has
a greater ability to disrupt asphalteneasphaltene and
asphaltenesubstrate interactions. The calculated molecular
weight data from the RI detector were calibrated against
polystyrene standards and are displayed in Table 2. In all cases
it appears that the HCB asphaltenes are signicantly smaller
than the unprocessed PRFR asphaltenes and have a narrower
molecular weight distribution, as expected. The signicantly
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Figure 8. SEC separation proles of PRFR and HCB heptane

asphaltenes dissolved in toluene at concentrations of 1% and 0.1%.
The data from the 0.1% toluene solutions are multiplied by 10 so that
the scale is more relevant.

Table 2. RI Data for 1% Solutions of HCB and PRFR

Heptane (C7) Asphaltenes Dissolved in THFa
sample

amount
injected

Mn

Mw

Mp

Mw/Mn

HCB C7 asphaltenes
PRFR C7 asphaltenes

40 L, 1.0%
40 L, 1.0%

158
714

535
5127

375
3186

3.39
7.18

Mn = number-average molecular weight, Mw = weight-average

molecular weight, Mp = molecular weight at peak maximum, Mw/Mn
= polydispersity or molecular weight range. Values are relative to
polystyrene standards.

Figure 7. Percent change in AD asphaltenes after adsorption with

PRFR plotted versus (top) the surface area of 25 mL of added sorbent,
(middle) the pore volume, and (bottom) the pore diameter of various
silica sorbents. The red squares are for the calcined silica extrudates,
and the blue diamonds are for the 10181, 646, 636, and Grace silica gel
sorbents.

Figure 9. TGA results for PRFR and HCB. Under these conditions the
onset of pyrolysis for PRFR was calculated to be about 430 C. Burno of carbon residue was carried out at 600 C instead of the typical
900 C.

mesh, and 3560 mesh. HCB was used, and adsorption was
carried out at 200 C for 0.5, 1, 2, 3, and 4 h. From these
experiments it is clear that smaller particles adsorbed more
asphaltenes and reached saturation sooner. This demonstrates
both shorter diusion times (or diusion distance) and less
pore plugging for smaller sized particles. Adsorption onto
whole alumina extrudates began to reach saturation at around 3
h, while the smaller 1435 mesh alumina began to reach
saturation around 2 h, and smallest 3560 mesh alumina
approached saturation in less than 30 min. The dierence in the
maximum amounts of asphaltenes adsorbed by the 1435
mesh and 3560 mesh particles is relatively small, with only a
4% increase in AD asphaltenes adsorbed after 4 h for the

smaller particles. However, with the much larger whole

extrudates after 4 h there was a tremendous dierence in the
amount of asphaltenes removed relative to the smaller particles:
4549% less asphaltenes were removed by the whole
extrudates. This signicant dierence shows that access to the
internal pore structure of whole alumina extrudates becomes
signicantly blocked by asphaltenes upon adsorption, which is
in line with other reports.22,23 Figure 10 shows the eect of
particle size and time on the removal of AD asphaltenes from
HCB.
Adsorption Capacity. AD data showed that 9.3 g of dried
Grace silica adsorbed about 50% of AD asphaltenes from 25.0 g
of HCB. HCB has about 9.6 wt % asphaltenes, which means
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taken into account when comparing the adsorption capacity in

this study to literature values: temperature, source of
asphaltenes, type of matrix dissolving the asphaltenes (solvent
or oil), and the solvent power of the matrix in which the
asphaltenes are dissolved.21 Besides these dierences, another
reason for the lower observed adsorption capacity may be that
HCB asphaltene molecules, and their resulting aggregates, are
inherently smaller because of the hydroconversion process,
which causes there to be more asphaltene molecules and
aggregates per unit weight than for unprocessed oils or mildly
processed oils.
Properties of Treated HCB. Viscosity. It is well-known
that as the amount of asphaltenes in oil decreases, the viscosity
decreases until the viscosity becomes dominated by the
molecular weight and composition of the maltenes.3538
Some have also observed that dierent asphaltene subfractions
can have very dierent eects on the viscosity of Canadian
bitumen.39 Likewise, in this study it was demonstrated that as
the amount of HCB AD asphaltenes decreased upon
adsorption, the viscosity also decreased with a reasonably
good linear relationship. HCB was treated to remove 79, 73, 66,
and 50% of the AD asphaltenes, and the viscosities of the
treated oils were measured using an oscillating piston
viscometer at 60 C. After removal of 79% of the AD
asphaltenes, the viscosity dropped from 3654 cP to 784 cP, a
likewise 78% decrease in viscosity. Of all the other AD ELSD
parameters, the amount of toluene-soluble asphaltenes was also
found to correlate best with the viscosity since it is the most
abundant asphaltene subfraction that is also most aected by
adsorption. The viscosities relative to the percent of AD
asphaltenes removed and toluene-soluble asphaltenes removed
are given in Table 3. Plots of the data with linear regressions are

Figure 10. Percent of AD asphaltenes removed after contacting HCB

with the same weight of whole alumina extrudates, 1435 mesh
alumina extrudates, and 3560 mesh alumina extrudates for 0.5, 1, 2,
3, and 4 h at 200 C.

that 25.0 g of HCB has about 2.4 g of asphaltenes. Removing

half of the asphaltenes, or 1.2 g, onto 9.3 g of Grace silica with a
surface area of 365 m2/g, gives a calculated adsorption capacity
of 0.35 mg/m2.
The adsorption capacity of Grace silica calculated from AD
data was further conrmed gravimetrically by two methods:
from the amount of 10 m heptane asphaltenes removed from
the treated HCB by gravimetric precipitation relative to
untreated HCB and from desorption of the adsorbed
asphaltenes bound to the Grace silica. From the rst method
it was determined that there was 11.53 wt % n-heptane
asphaltenes in the original oil and after treatment there was
6.44 wt % asphaltenes. This translates to 1.27 g of asphaltenes
still remaining in the 25 g of treated HCB after treatment with
25 mL of Grace silica. This gives an adsorption capacity of 0.37
mg/m2. In the second method, spent Grace silica was ltered
from the treated oil and rinsed with toluene several times until
the toluene became light yellow. AD data showed that the
composition of the residue recovered from the toluene ltrate
had the same composition as the treated oil originally ltered
from the reactors, demonstrating that no additional asphaltenes
were precipitated on, or desorbed from, the surface of the spent
Grace silica. The dried toluene-rinsed spent Grace silica was
Soxhlet-extracted with 90:10 (v/v) NMP/n-butylamine solution until the extracts became colorless. The volatiles were
removed from the extracts, and they were dried in a vacuum
oven. The weight of asphaltenes was determined from the
dierence in the weights of the dried toluene-rinsed spent
Grace silica and the dried Grace silica after desorption with
NMP/n-butylamine. This method gave 1.15 g of asphaltenes
desorbed from Grace silica, corresponding to an adsorption
capacity of 0.34 mg/m2, which is in agreement with the other
methods.21 Material balance of the treated oil, Grace silica, and
desorbed asphaltenes was carried out in duplicate and gave
closure with less than 0.1 wt % of material lost.
The adsorption capacity of HCB asphaltenes onto Grace
silica is an order of magnitude smaller than the maximum
adsorption capacities reported in the literature for asphaltene
adsorption onto hydrophilic silica (3.78 mg/m2) and the
theoretical maximum of 3.6 mg/m2 based upon a continuous
homogeneous monolayer of asphaltene aggregates 3 nm high
with a density of 1200 kg/m2.34 Several considerations must be

Table 3. Viscosities Measured at 60 C Using a VISCO PRO

Piston Viscometer for HCB Treated with Various Sorbents
at 200 C for 4 h and Respective Values of the Percentages
of AD Asphaltenes Removed and Toluene-Soluble
Asphaltenes Removed

original
HCB
reaction
control
after
adsorption
after
adsorption
after
adsorption
after
adsorption

% toluene-soluble
asphaltenes removed

% AD
asphaltenes
removed

viscosity @ 60
C (cP)

0.00

3652

3537

48.50

50

1442

62.86

66

1465

71.56

73

1242

78.60

79

784

given in Figure 11. Interestingly, in all sets of experiments a

slight decrease in the amount of AD asphaltenes and viscosity
was observed after the oil was heated without any sorbent
relative to the unheated oil.
Heithaus Titration/Automatic Flocculation Titration
(WRI). A common method used to probe the colloidal stability
of asphaltenes in oil is to titrate the oil with a precipitant (poor
solvent) until the asphaltenes become destabilized and
occulate from solution; this can be done with or without
dissolving the oil in a good asphaltene solvent prior to the
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Table 4. Selected AFT Values for HCB with Various

Amounts of Asphaltenes Removed by Adsorption onto
Grace Silica Gel at 200 C for 4 ha
g of HCB:
mL of Grace silica

% AD asphaltenes
removed

FRmax

1/
Xmin

P
value

R2

25:0
45:5
40:10
35:15
30:20
25:25

6.8
14.0
21.1
25.3
37.6

63.4
59.1
53.7
53.1
54.1
51.1

22.5
13.2
15.5
4.8
3.5
4.0

1.04
1.08
1.06
1.21
1.29
1.25

0.9400
0.8826
0.9951
0.9836
0.9499
0.9662

Titrations were carried out at 50 C with solutions of treated oil

dissolved in 1-methylnaphthalene and titrated with hexadecane.

Figure 11. Viscosity measured at 60 C as a function of AD

asphaltenes removed (blue) and toluene-soluble asphaltenes removed
(red).

CHNOS and Metals Analysis. Compared with that of

untreated HCB, the elemental analysis of HCB (25 g) treated
with Grace silica gel (25 mL) to remove 50% of the AD
asphaltenes produced an oil with signicantly reduced carbon
and nitrogen, an increased amount of hydrogen, and decreased
Ni and V contents. Several publications have shown similar
correlations, especially with decreases in nitrogen, oxygen, and
aromaticity upon adsorption.21 In this study, the oxygen
content was not aected by adsorption since nearly all of the
acidic carboxylate functional groups were denatured during the
hydrotreating process.26 This is evidenced by the very low total
acid number (TAN) values obtained for HCB. Elemental
analyses for CHNOS and Ni and V for the separate batches of
samples treated similarly are given in Table 5. The CHNOS
analyses were performed on treated oils that had been ltered
through a 60 or 100 mesh screen to remove sorbent
particulates.
Total Acid and Base Contents. TAN titrations were carried
out on both untreated HCB and PRFR samples, samples
treated with Grace silica gel (25 g of oil to 25 mL of sorbent),
and heated controls (200 C for HCB and 300 C for PRFR).
Treatment of PRFR with Grace silica to remove 38% AD
asphaltenes also removed over half of the acid content:
untreated PRFR had a TAN of 4.14 mg of KOH/g, and treated
PRFR had a TAN of 1.99 mg of KOH/g. The reduction in
acidic species is consistent with literature reports showing that
acidic, and particularly carboxylic groups, are removed by
adsorption.21 For HCB, however, because of the very small
initial TAN (0.12 mg of KOH/g), no change was observed
after removal of asphaltenes by adsorption. The TAN values
did not vary signicantly between the untreated original oils
and the heated reaction controls.
With regard to the bases, there was a signicant reduction
after adsorption for both HCB and PRFR. For PRFR the total
base number (TBN) was reduced by 22%, from 4.17 to 3.25
mg of KOH/g. A slightly more dramatic reduction was seen for
HCB, which showed a drop of 32% in the TBN after
adsorption, from 9.95 to 6.79 mg of KOH/g. The greater
amount of basic nitrogen in HCB compared with PRFR is likely
due to the thermal stability of basic components, which usually
become enriched in cracked streams.3033 Signicant removal
of basic nitrogen is consistent with previous ndings suggesting
that the partial positive charge of basic nitrogen groups is
strongly attracted to negatively charged surfaces such as silica
gel45 and that more specic interactions occur between the
surface acidic SiOH groups and molecules containing basic
nitrogen.

titration. At a constant temperature and titration rate, the point

at which asphaltenes begin to occulate is known as the onset
of occulation, and it is dependent upon both the solubility of
the asphaltenes and the solvent strength of the supporting oil
matrix. Besides the oil components, quantication by this
method is contingent upon the solubility parameters of the
solvent and titrant. This method was rst developed by
Heithaus40 and has been further developed by others, including
WRI.4144 The WRI automated occulation titrimeter (AFT) is
a continuous titration method that uses an optical absorbance
detector set at 740 nm to detect scattering of particles and
identify the point of occulation.
HCB is a severely hydroconverted oil that has been
processed up to the threshold of stability, meaning that the
asphaltenes are on the cusp of precipitation. In order for
occulation titration data to be valid, for self-incompatible oils
or nearly incompatible oils the dissolving solvent and
temperature must be sucient to dissolve all of the
asphaltenesno occules should be present (in some cases,
addition of relatively good solvents can actually lead to
occulation). For this reason, 1-methylnaphtalene solvent
(Hildebrand solubility parameter = 20.1 MPa1/2) was used as
the good solvent, which was titrated with hexadecane
(Hildebrand solubility parameter = 16.3 MPa1/2), similar to
the Shell/Zematra method (as described in ASTM D7060).
The titration rate was set to 0.10 mL/min, and the sample
temperature was set to 50 C. Titrations were carried out on
the original HCB and HCB treated with the following ratios of
Grace silica (g of HCB:mL of sorbent): 45:5, 40:10, 35:15,
30:20, and 25:25. For untreated HCB a P value of 1.04 was
obtained with a good linear correlation. Since the minimum
theoretical P value is 1.00, this represents an oil with very low
stability. Each titration was carried out in duplicate, and the
various titration parameters (FRmax, 1/Xmin, P value) and linear
regression coecients (R2) are given in Table 4 for the same oil
sample at three dierent concentrations. Untreated HCB has a
P value of 1.04, and upon treatment of the oil by adsorption the
P value reached as high as 1.29. Likewise, as the occulation
ratio (FRmax is the y intercept) and 1/Xmin (Xmin is the x
intercept) decrease, the quality of the oil improves. These data
show how the asphaltenes appear to be more easily dissolved by
the oil matrix and the dissolving power of the oil improves with
increased adsorption, thus improving the overall stability of the
oil. Others have observed similar improvements in the P value
after treatment of oil by adsorption.32
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Table 5. Elemental CHNOS and Ni and V Analyses for Three Separate Batches of Treated HCB (50% Asphaltenes Removed)
and Untreated HCB Samples (Data for Dierent Batches Are Separated by Horizontal Lines)
untreated
treated
untreated
treated
untreated
treated

CHNOS total

H/C

% AD asphaltenes removed

Ni (ppm)

V (ppm)

86.86
86.69
86.95
86.74
86.86
87.12

9.42
9.78
9.59
9.79
9.32
9.56

0.83
0.66
0.83
0.70
0.81
0.71

0.66
0.66
0.66
0.64
0.69
0.65

2.04
1.99
2.26
2.33
2.18
2.16

99.81
99.78
100.29
100.20
99.86
100.20

1.30
1.35
1.32
1.35
1.29
1.32

50

48

48

40
31
52
26
50
24

77
64
81
56
83
41

Thermogravimetric Analysis. TGA is useful for determining

the amount of volatiles in oil, the boiling points of heavier ends,
the amount of material that can undergo pyrolysis via aliphatic
cleavage, the amount of microcarbon residue, and the ash (or
inorganic) residue remaining after the oxidative burn-o. As
expected, relative to those for untreated HCB, the TGA results
for HCB treated with Grace silica gel (50% AD asphaltenes
removed) showed an increase in volatiles (1.5 wt %) and
pyrolysis material (9 wt %) and a decrease in the microcarbon
residue by 29 wt %. The TGA results imply that HCB treated
with sorbents will have better thermal stability and give higher
liquid yields and less coke relative to untreated HCB.
Asphaltene Determinator Coke Index. Previous work has
shown that pyrolysis/cracking of dierent residua under an
inert atmosphere causes the cyclohexane-soluble asphaltenes
decrease and the more polar and aromatic methylene chloridesoluble (precoke-like) asphaltenes to increase because of
dealkylation.27,46 Relative to the toluene-soluble and methylene
chloride-soluble asphaltenes, the cyclohexane-soluble asphaltenes contain signicantly more aliphatic groups and a lower
aromaticity. The study also showed that during pyrolysis, as the
fraction of cyclohexane-soluble asphaltenes approaches that of
methylene chloride-soluble asphaltenes, the oil becomes
increasingly unstable, indicating the onset of coke formation.
This crossover point is dened as the AD Coke Index, and it
appears at about 1 for the ELSD and 2 for the 500 nm optical
absorbance detector.27 Therefore, decreasing the amount of
methylene chloride-soluble asphaltenes by adsorption, especially compared with the cyclohexane-soluble asphaltenes,
indicates that an oil becomes more stable with regard to
pyrolysis and coke formation.27,46
The HCB in this study is residua from severe hydroprocessing, which tends to change the size and aromaticity of
the molecules compared to milder cracking in the absence of a
catalyst and hydrogen.26 Because of this, the cuto points for
the AD Coke Index for HCB are not expected to correspond
exactly to those in previous residua studies. As evidence of this,
HCB that had been processed to the verge of stability had an
AD Coke Index of around 0.1 for the ELSD and around 0.3 for
the 500 nm detector. The ELSD values are considered to
contain more error than the 500 nm data since the amount of
cyclohexane-soluble material in the oil is very low, approaching
the detection limit (and nonlinear region) of the ELSD.
Despite this fact, the data from the ELSD and 500 nm detectors
show roughly the same trend but to dierent degrees: upon
increased adsorption onto Grace silica, the precoke-like
methylene chloride-soluble asphaltenes are more selectively
removed than the more aliphatic cyclohexane-soluble asphaltenes (Figure 12). This shows that removing more asphaltenes
by adsorption onto silica gels does selectively improve the
thermal stability of HCB with respect to coke formation.

Figure 12. Plots of the AD Coke Index for the ELSD and 500 nm
detector for HCB treated with Grace silica at 200 C for 4 h at the
following ratios: 40:10, 35:15, 30:20, and 25:25 (w/v).

Asphaltene Subfraction Selectivity. As an overview, the

Asphaltene Determinator provides a rapid and reliable way to
quantify changes that occur with asphaltenes in oil, especially
changes due to adsorption or thermal processes. The AD is set
up with an ELSD, which provides an approximate weight
percent of the material that reports to each solvent fraction, and
absorbance detectors (500 and 700 nm), which provide the
concentrations of colored aromatic materials (usually containing heteroatoms) in the dierent solvent fractions. The AD
method takes asphaltenes and fractionates them into cyclohexane-, toluene-, and methylene chloride-soluble asphaltenes.27 In the analysis of whole oils, the heptane-soluble
material is simply the maltenes. For the asphaltenes, as the
solvent strength increases (cyclohexane < toluene < methylene
chloride), the asphaltenes that report to those fractions also
increase in polarity and aromaticity.27,46 Pyrolysis studies using
various vacuum residua have shown that upon thermal cracking,
the least aromatic cyclohexane-soluble asphaltenes become
depleted by cleavage of aliphatic moieties to form less soluble
and more aromatic toluene-soluble and methylene chloridesoluble asphaltenes.27 One of the goals of this research was to
determine whether treating HCB by adsorption could
selectively remove the most polar and aromatic toluene-soluble
and especially methylene chloride-soluble asphaltenes while
leaving behind the cyclohexane-soluble asphaltenes, since they
can be further upgraded and may enhance the oils stability. To
gain a broader understanding of how the asphaltene
subfractions change upon adsorption for HCB, the evolution
of the various asphaltene subfractions is reported for all of the
dierent sorbents surveyed during this study using the same
loading (25 g of HCB with 25 mL of sorbent) and conditions
(200 C, 4 h). Following the ELSD data for the various AD
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their quantication by the ELSD less certain due to the

detection limit (and nonlinear region) of the detector.
The relative concentration of the cyclohexane-soluble
asphaltenes (or relative amount of colored material) can be
better quantied using the 500 nm absorbance detector data.
Previous studies have shown that upon pyrolysis/cracking, in
the absence of hydrogen, the cyclohexane-soluble asphaltenes
decrease as a result of dealkylation and the methylene chloridesoluble asphaltenes increase.27,46 The 500 nm AD data from all
of the HCB adsorption experiments under the same loading
and conditions show that the cyclohexane-soluble asphaltenes
increase after adsorption while the methylene chloride-soluble
asphaltenes decrease. Figure 15 shows how the various AD
subfractions change upon adsorption using 500 nm data: the
heptane-soluble material and cyclohexane-soluble asphaltenes
increase, and the toluene- and methylene chloride-soluble
asphaltenes decrease.
For HCB under these conditions, the AD data clearly show
that the most aromatic toluene- and methylene chloride-soluble
asphaltene fractions are selectively adsorbed. This is ideal
because it leaves behind the cyclohexane-soluble asphaltenes
which are more benign and contain more aliphatic groups,
which can add value for additional upgrading.
Sorbent Regeneration. A fundamental aspect for
developing a commercially viable adsorption process is that
the sorbent be amenable to several regeneration cycles without
a signicant reduction in performance. Of the various
regeneration methods available solvent desorption was studied
in detail. After treating HCB with Grace silica (1:1 w/v), the
spent Grace silica was collected by ltering it through a 60
mesh screen. Excess HCB residue that remained on the surface
of the sorbent and inside the pore volume of the sorbent was
removed by rinsing the spent Grace silica several times with
ambient-temperature toluene until the toluene extracts became
pale yellow. By AD analysis, the asphaltene content of the oil
rinsed from the spent Grace silica was the same as that of the
treated oil that was initially ltered from the spent Grace silica.
This showed that all of the entrained treated oil had been
removed from the silica and that no desorption of adsorbed
asphaltenes had occurred. After several Soxhlet extractions with
various solvent mixtures were performed, it was determined
that NMP containing 10% n-butylamine was highly eective at
removing adsorbed HCB asphaltenes (Figure 16).
To determine whether regenerated Grace silica could be used
for successive adsorption experiments, several batches of
regenerated Grace silica were prepared by NMP/n-butylamine
Soxhlet extractions. The regenerated Grace silica was contacted
with fresh HCB, and the adsorption experiments were carried
out in batches as before. The AD results showed that an
average of about 47% AD asphaltenes were removed, indicating
no signicant decrease in the adsorption capacity using the
regenerated Grace silica. The Grace silica was regenerated a
second time and a third time using the same method. The
amount of asphaltenes adsorbed during the second regeneration was slightly lower than expected, but upon the third
regeneration cycle the AD data again showed that 47% of AD
asphaltenes were removed. The anomaly in the second set of
regeneration experiments was not further investigated but may
have been due to some entrained desorption solvent mixture
remained in the sorbent. A summary of the amounts of AD
asphaltenes removed during the regeneration experiments is
given in Figure 17. These results show that it is possible to

asphaltene subfractions revealed that the toluene-soluble

asphaltenes decreased linearly and the heptane-soluble material
increased linearly with increased adsorption (Figure 13).

Figure 13. AD data showing the percent change in (top) heptanesoluble material and (bottom) toluene-soluble asphaltenes relative to
the change in the AD asphaltenes after adsorption of asphaltenes from
HCB. Adsorption is increasing from right to left in the plots. The data
are relative to respective control experiments. The data are from all of
the various sorbents used at the same HCB:sorbent ratio (25 g:25 mL)
at 200 C with a contact time of 4 h.

Upon adsorption, the AD data also showed a consistent

decrease in the most polar and pericondensed aromatic
methylene chloride-soluble asphaltenes (Figure 14). Since the
HCB had been severely hydroprocessed, they contained a very
small amount of cyclohexane-soluble asphaltenes. This made

Figure 14. AD data showing the percent change in methylene

chloride-soluble material relative to the change in the AD asphaltenes
after the adsorption of asphaltenes from HCB. The data are relative to
respective control experiments. The data are from all of the various
sorbents used at the same HCB:sorbent ratio (25 g:25 mL) at 200 C
with a contact time of 4 h.
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Figure 15. AD data for the 500 nm detector for the percent change in the various AD subfractions relative to the percent change in ELSD AD
asphaltenes for HCB treated with dierent sorbents. All of the data are relative to respective control experiments. The data are from all of the various
sorbents used at the same HCB:sorbent ratio (25 g:25 mL) at 200 C with a contact time of 4 h.

Figure 17. Average percent of AD asphaltenes removed from HCB for

three regeneration cycles of spent Grace silica. The initial amount of
asphaltenes removed from fresh Grace silica was around 48%.

Figure 16. (left)Spent Grace silica that was rinsed with toluene to
remove entrained treated oil and then was Soxhlet-extracted with 10%
(v/v) n-butylamine in NMP and (right) the same material Soxhletextracted with NMP alone.

CONCLUSION
By size-exclusion chromatography and thermogravimetric
analysis it was shown that the LC-ner hydroconversion
process produces much smaller HCB asphaltenes compared
with unprocessed PRFR asphaltenes. These smaller asphaltene
molecules contain less sterically hindering alkyl side chains,
allowing them to be more eciently adsorbed into sorbents
with smaller pore diameters compared with PRFR asphaltenes.
In general, it was show for silica sorbents that HCB asphaltene
adsorption increased with increasing surface area as long as the
pore diameter was suciently large to allow ecient diusion
of the asphaltene molecules. On the other hand, adsorption of
PRFR asphaltenes decreased with increasing surface area but

reuse Grace silica after desorption of adsorbed asphaltenes for

additional cycles.
Since the AD data for the treated HCB showed that
asphaltene adsorption preferentially adsorbs less soluble
asphaltenes, it is expected in turn that the asphaltenes desorbed
from the spent Grace silica should likewise be enriched in the
less soluble asphaltenes. AD analysis was carried out on HCB
asphaltenes precipitated with heptane and compared with
asphaltenes desorbed from the Grace silica. The data showed
that the desorbed asphaltenes had signicantly less of the more
soluble asphaltenes and signicantly more methylene chloridesoluble asphaltene (Figure 18).
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Article

ACKNOWLEDGMENTS
We are grateful to Shell for providing funding and allowing
publication of this work. The authors also acknowledge Dr.
Nihar Phalak for reviewing the manuscript and productive
discussions and Mark Sanderson and Justin Boysen for
performing laboratory work.

Figure 18. Comparison of AD ELSD data for asphaltenes precipitated

from HCB using heptane, and HCB asphaltenes desorbed from spent
Grace silica that was prerinsed with toluene to remove entrained
treated oil.

increased with increasing pore diameter. The much larger

PRFR asphaltenes were signicantly more sensitive to the pore
diameter of the sorbents than HCB asphaltenes. Another
dierence between the adsorption behaviors of the processed
oil and unprocessed oil was that the optimal asphaltene
adsorption from HCB occurs at a signicantly lower temperature than for the PRFR bitumen. For HCB, as the particle size
of the sorbents was decreased (by crushing and sieving), the
overall amount of asphaltenes adsorbed increased and
saturation was reached more quickly. This demonstrates that
for larger sorbent particles the diusion of asphaltenes to the
surface area of the internal pore volume becomes restricted and
signicant pore plugging takes place.
The spent Grace silica gel sorbent was successfully
regenerated to its initial adsorption capacity by desorbing the
asphaltenes using a mixture of NMP and n-butylamine. By
calculating the adsorption capacity from three dierent
methods, it was determined that Grace silica gel has a capacity
to adsorb about 0.340.37 mg of HCB asphaltenes per square
meter of sorbent.
Removing about 50 wt % of the asphaltenes from HCB
signicantly reduced the viscosity of the treated oil by about
50%, reduced the TBN by 32%, reduced (Ni + V) by about
40%, and reduced the carbon residue by almost 30 wt %. The P
value was also improved to 1.29 from 1.04, and the 500 nm AD
Coke Index was signicantly improved from 0.35 to 1.22. The
increased Coke Index indicates that the thermal stability of the
treated HCB was greatly improved with respect to formation of
coke upon pyrolysis. The AD asphaltene solubility proles
showed that the more aromatic toluene- and methylene
chloride-soluble asphaltenes were preferentially adsorbed
relative to the less aromatic cyclohexane-soluble asphaltenes.
Taken all together, these data show that asphaltene adsorption
signicantly improves the quality of HCB by removing
poisoning contaminants, increasing thermal stability, and
reducing coke product yields.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: Jeramie.adams@uwyo.edu.
Notes

The authors declare no competing nancial interest.

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