ARTICLE

pubs.acs.org/EF

Suitable Density Determination for Heavy Hydrocarbons by

Solution Pycnometry: Virgin and Thermal Cracked Athabasca
Vacuum Residue Fractions
Lante Carbognani,* Lante Carbognani-Arambarri, Francisco Lopez-Linares, and Pedro Pereira-Almao
Alberta Ingenuity Centre for In Situ Energy (AICISE), Department of Chemical and Petroleum Engineering, Schulich School of
Engineering, University of Calgary, Calgary, Alberta T2N 1N4, Canada

ABSTRACT: Density is an important parameter for understanding molecular packing, stability, and reactivity of petroleum
fractions. The determination of density for extremely viscous residual fractions measured at high temperature (reduced viscosity) is
dicult and prone to error if results are extrapolated to lower temperature ranges. This problem is addressed in the present study
with fractions derived from virgin and visbroken Athabasca vacuum residua. Solution pycnometry (toluene solvent) was studied and
demonstrated a feasible, fast, simple, and reliable technique, applicable to a wide variety of petroleum materials, including
asphaltenes and vacuum residua. Reported densities were aected to the third decimal position [American Petroleum Institute
(API) gravities found reliable to (0.15 API]. The density for mixtures of residual oil fractions was determined to be an additive
property. Athabasca vacuum residue solvent deasphalting and thermal cracked fractions are studied. Thermal cracking was observed
to increase asphaltene densities to values as high as those displayed by coals, suggesting that highly aromatic-condensed structures
represent these species better. Further application of the methodology is illustrated by monitoring Athabasca bitumen upgrading at
bench scale.

1. INTRODUCTION
Bulk density for hydrocarbon fractions is an important parameter
for understanding stability issues of dense asphaltenes,1 correlations
between carbon content, density, porosity, and gasication reactivity
of coals,2 and assessing oxidation/cracking balances during asphalt
oxidation.3 Density has been found as a convenient tuning para-
meter for building representative average molecular structures via
molecular dynamics simulation.4 Density changes has been de-
scribed for detection of onset precipitation of solids.5
Methods for density determination of petroleum and derived
products based on dierent properties have been standardized, as
described by Speight.6 Dierent measurement principles are
described within these standard procedures, among them: hy-
drometry (ASTM D287, ASTM D1298, ASTM D1657, and IP
160), pycnometry (ASTM D70, ASTM D941, ASTM D1217,
ASTM D1480, and ASTM D1481), uid displacement (ASTM
D712), digital density meter (ASTM D4052 and IP 365), and
digital density analyzer (ASTM D5002).
When solid samples or extremely viscous materials, such as
vacuum residua, are the analytes of interest, serious drawbacks
arise because low viscosity (uidity) is required for determina-
tions using these systems. High temperatures can be set up for
bringing samples to uidity. Vacuum residua normally become
mobile in the 120
150 C range. Asphaltenes normally liquefy
above 205 C.7 However, nonlinear extrapolation of densities
from these temperature ranges to routine ambient set points, i.e.,
15
25 C, is a serious drawback from using high temperatures
during the measurements.8 Instead, wide-mouth glass pycn-
ometers and water + surfactant as a displacing uid are standard
techniques described for solid asphalts.9 However, nonmiscible
displacing uids, such as water or n-heptane, have been deter-
mined to pose several problems as well as trapped gas bubbles
release. Gas (helium) pycnometers have also been described for
both types of solid or viscous materials.10,11 Helium pycnometry
is accepted to provide true densities of solid materials, such as
coals, because this probe of small-molecular dimensions guaran-
tees its access to the whole porous space of samples and is a non-
interacting uid with the solid matrix.12,13
Aiming to run several samples simultaneously at near ambient
conditions (15
25 C temperature range), glass pycnometry was
evaluated during this work for the determination of density of
cumbersome materials, such as sticky vacuum residua and solid
asphaltenes. The present work contemplates the use of a uid able
to dissolve the analytes of interest, aiming to provide the following
solutions: (1) Overcoming the solid/sticky nature of the samples,
(2) use of small samples, (3) simultaneous determination of several
samples, (4) simplicity and inexpensive assemblies implied, and (5)
reasonable accuracy and precision. Toluene was determined to be a
convenient solvent for the intended goal. Determined densities
were found accurate to the third decimal position, variability that
was found enough for monitoring purposes. Several applications
are described in this paper with Athabasca bitumen-derived frac-
tions; in particular, the eect from mild thermal cracking on
Athabasca residua asphaltenes was studied in greater detail.
2. EXPERIMENTAL SECTION
2.1. Studied Samples. Selected samples from bench-scale experi-
ments were studied in this work. These will be directly described within
the Results and Discussion.
Received: May 25, 2011
Revised: July 11, 2011
Published: July 15, 2011

r 2011 American Chemical Society 3663 dx.doi.org/10.1021/ef200780d | Energy Fuels 2011, 25, 36633670
Energy & Fuels ARTICLE

Table 1. Densities for Reference Materials

accepted density determined density (toluene
analyte analyte group type origin temperature (C) [(g/mL at T (C)] solvent; g/mL at T (C)]

light GO oil distillate Athabasca bitumen 15.6 0.9031a 0.9023

atmospheric GO Athabasca bitumen 15.6 0.9212a 0.9201
vacuum GO Lloydminster bitumen 15.6 0.9605a 0.9612
n-heptane apolar liquid Sigma-Aldrich (P/N 32287) 15.6 0.6871a 0.6885
o-xylene Sigma-Aldrich (P/N 34886) 15.6 0.8833a 0.8821
1-methyl-naphthalene Sigma-Aldrich (P/N MS7006) 20 1.0058b 1.0127
nahpthalene apolar solid Sigma-Aldrich (P/N 147141) 20 1.0253b 1.0349
uorene Aldrich (P/N 12.833-3) 20 1.1749c 1.0878
biphenyl Fisher (P/N 0-1421) 20 1.04b 1.0420
phenantrene Sigma-Aldrich (P/N 11409) 23 1.1793c 1.1386
phenantrene Sigma-Aldrich (P/N 11409) 25 1.1749c 1.1970d
b
pyrene Sigma-Aldrich (P/N185515) 23 1.271 1.2033
butyl-acetate polar liquid Aldrich (P/N 40284-2) 23 0.8781a 0.8800
butyl-acetate Aldrich (P/N 40284-2) 15.6 0.8839a 0.8870
1-octanol Fisher (A-402) 23 0.8230a 0.8185
1-octanol Fisher (A-402) 15.6 0.8289a 0.8241
2-methoxy-methyl-ethyl ether Aldrich (P/NM1410-2) 23 0.9477a 0.9484
2-methoxy-methyl-ethyl ether Aldrich (P/NM1410-2) 15.6 0.9538a 0.9589
3-pentanone Aldrich (P/N 12760-4) 23 0.8112a 0.8184
benzophenone polar solid BDH (P/N 273381) 18 1.111b 1.1295
camphor Fluka (P/N 21300) 25 0.99b 0.9609
camphor Fluka (P/N 21300) 23 0.9649c 0.9628
acridine Fluka (P/N 01640) 20 1.005b 1.1971 (avg)
acridine Fluka (P/N 01640) 20 1.005b 1.2694c
acridine Fluka (P/N 01640) 20 1.005b 1.0114d
a b c d
Neat. Handbook (see ref 21). C7-displacer pycnometry (see refs 1 and 4). MeOH solution pycnometry.

Deasphalted oils (DAOs or maltene fractions) and asphaltene
fractions isolated from virgin and thermal cracked Athabasca vacuum
residua are also studied. Mild thermal cracking (visbreaking) for these
samples was previously reported.14 n-Heptane (nC7) and n-pentane
(nC5) alkane precipitants were used during deasphalting operations,
with experimental deasphalting conditions being reported before.14
Isolated asphaltenes were not solvent-washed. Washing is reported to
change asphaltene properties, depending upon the washing approach
followed.15
One set of C7-precipitated Venezuelan asphaltenes was analyzed by
glass pycnometry with three dierent displacing uids: n-heptane,
acetonitrile, and helium. Asphaltene properties and origin can be found
elsewhere.16,17 Pycnometry using non-solvent displacer uids was
reported for the studied Venezuelan asphaltenes,1,4 and helium pycno-
metry for selected samples was carried out within IFP facilities at Rueil-
Malmaison (Paris, France).18 Asphaltene samples from the 550 C+
vacuum residue from Venezuelas Cerro Negro heavy petroleum have
been analyzed for solvent swelling19 and are discussed within the Results
and Discussion in the present study.
2.2. Glass Pycnometers. Two commercially available glass pycn-
ometers were used in this study. Both are glass systems of about 11 mL
capacity. The more complex device (model 1) is provided with an
internal temperature probe (thermometer), manufacturers P/N 16628
029 (KIMAX) and 15123R-10 (KIMBLE-CHASE). The simpler model
(2) is manufactured by ACE Glass Incorporated (NJ, P/N 5475-05).
More details on pycnometry were recently disclosed.20
2.3. Pycnometer Calibration. Deionized water was used for
pycnometer calibration. Its density values taken from the literature21 at
10, 20, 30, 50, and 70 C are 0.9997, 0.9982, 0.9957, 0.9980, and 0.9778
g/mL, respectively. Water density at 15.6 C was calculated to be 0.9990
g/mL, by interpolation. A Mettler model AB304-5 balance accurate to
0.1 mg was used for all determinations.
2.4. Solvents. Toluene [high-performance liquid chromatography
(HPLC) grade, >99.9%] from Sigma-Aldrich (P/N 354866-44L)
was used as a solvent medium for the present study. CHCl3 (>99.8%,
Sigma-Aldrich, P/N 480150-4L), tetrahydrofuran (THF, >99.0%,
Sigma-Aldrich, P/N 360589-4L), and n-heptane (Sigma-Aldrich,
P/N 32287) were used as received for comparison to toluene-
determined density values.
2.5. Thermostated Recirculating Bath. A VWR 28 L refriger-
ated recirculator bath model 1180S was used for this study. The
temperature can be controlled to (0.1 C. Deionized water was used
as recirculation fluid. This particular bath allows for inclusion of up to 40
pycnometers for carrying out simultaneous determinations; however,
reasonably only six can be simultaneously handled by a single operator in
a routine analysis session.
2.6. Reference Materials. Three bitumen distillates and several
commercially available standard compounds were selected for validation
of determined densities via toluene pycnometry. Table 1 presents the
origin and properties for these reference materials.
2.7. Routine Pycnometry Protocol. About 2
3 g of vacuum
residua or 1.5 g of asphaltenes were weighted (to the nearest 0.1 mg)
inside 20 mL and/or 2 ounce vials. About 5 mL of toluene was added,
and the vials were then capped. A battery of samples was prepared, and
the vials were left overnight in a shaker. Quantitative transfer of the
solutions was achieved by repeated toluene rinsing (about 5  0.5 mL).
Pycnometers were sonicated for a couple of minutes in an ultrasound
bath (Branson model 3510). Pycnometers were immersed in the

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Energy & Fuels
thermostatted bath, and achievement of the setup temperature was
verified with one model 1 pycnometer filled with toluene for such a
purpose. Thermostating is usually performed for about 30 min. During
this period, repeated toluene additions were systematically carried out
over each pycnometer with the aid of a syringe and needle inserted
though the capillary tube. When pycnometers were thermostatted and
totally filled, they were capped, dried, and weighted. Density values [at T
(C)] were determined using eq 1
s m=Pv
tm=t 1
where s is the sample density (g/mL), m is the sample mass (g), Pv is
the pycnometer volume (mL, determined with water), tm is the toluene
mass (g), t is the toluene density (g/mL), and T is the temperature
Specic gravity (60/60 F) was calculated correcting determined
density values by water density at 60 F (15.6 C), and this parameter
was used for determining American Petroleum Institute (API) gravity
using eq 2. Density reported as API gravity follows a modied Baume
scale, with this being common practice within the oil industry.6
API gravity deg 141:5=specific gravity at 60=60 F
131:5
2 such as n-heptane, the common precipitant alkane used for
2.8. Bitumen Upgrading Conversion. Heavy end conversions
during upgrading studies of a wide range distillation cut and one thermal
cracked residue were defined via high-temperature simulated distillation
(HTSD). The Athabasca 250
516 C fraction was the selected
distillate. The Athabasca vacuum residue thermal cracked under differ-
ent severities was the residual studied sample. ASTM D7169 was
adopted for these calculations.22 Equation 3 presents how conversion
is calculated for fractions boiling above one set temperature limit when
converted into lighter distillates.
percent weight conversion percent weight IBP > T C in feedstock

percent weight IBP > T C in product
=percent weight IBP > T C in feedstock  100 3
where IBP is the initial boiling point and T is the temperature cut point.
2.9. Viscosity Determination. Reported viscosities were deter-
mined with a cone-plate Brookfield viscometer model RV DV-II
+PROCP. Setup temperatures were maintained with a recirculating
glycol bath (Brookfield model TC-102).
2.10. Microcarbon (MCR) Analysis. MCR was determined
following a published in-house procedure.23
3. RESULTS AND DISCUSSION
3.1. Proposal of Solution Pycnometry for Density Deter-
mination of Solid/Viscous Petroleum Samples. Routine
practiced hygrometer24 and digital densimeter25 density deter-
minations are not suitable for extremely viscous materials, such
as oil vacuum residua, unless high temperatures are set up for
bringing samples into the liquid phase. Fluidification for these
samples requires temperatures in the 120
150 C range for oil
residua and more than 200 C for asphaltene samples.7 Extra-
polation of densities determined around these temperatures to
routine ambient ranges (15
25 C) is not straightforward.
Reportedly, nonlinear effects preclude reliable and easy achiev-
able linear extrapolation.8 Gas pycnometry has been described
for coping with the cited problems, with applications being
described in the literature.10
13 However, this technique is
more complex, expensive, and nonroutine in most petroleum
laboratories.
ARTICLE
Figure 1. Densities for nC7-precipitated asphaltenes. Results were
determined with helium or glass pycnometry with nC7 and CH3CN
uids. Analyzed Venezuelan asphaltenes are described elsewhere.16
18
Use of non-solvent displacer uids in glass pycnometry has
been standardized for asphalt samples, selecting water plus a
wetting surfactant as the displacing uid.9 Also, a non-solvent,
deasphalting, has been described in the literature for pycnome-
try density determination.1,4 However, these pycnometry meth-
ods based on water or non-solvent displacer liquids have been
found to randomly fail from a series of causes. First, lling
pycnometers with highly viscous and sticky materials, such as
some oil residua, is extremely cumbersome. Second, releasing
trapped air bubbles proved dicult, even submitting the mix-
tures to ultrasonication. One further drawback of using non-
solvent displacer uids is the fact that density values determined
with dierent uids have been observed to dier. One set of
asphaltene samples was analyzed by helium pycnometry plus
glass pycnometry with n-heptane and acetonitrile. Figure 1
presents the ndings from these experiments. Samples analyzed
with helium and nC7 were observed to display higher values
when the data were gathered by gas pycnometry. These results
are a priori expected, because the displacer uid (helium) is an
small molecule able to penetrate the whole porous space of the
samples, independent of pore sizes or interlamellar spacing.12,13
Size eects have been reported during density determination of
coal samples with dierent uids.2,12 On the other hand, the set
of samples analyzed with nC7 and CH3CN displacer uids
showed an opposite trend; i.e., density results achieved with
acetonitrile were lower compared to those obtained with nC7.
These results are contrary to the expectations based on the
estimated lower molecular cross-section for CH3CN. However,
non-size eects, such as these determined with asphaltene
samples, have been reported for coals determined with metha-
nol, hexane, and mercury,26 and even with hydrogen that
reportedly is able to become adsorbed over coal samples.12
Complex interactions, such as those observed herein, have been
described in experiments in which carbon nanotubes are lled
with water and acetonitrile, showing varying interactions that
depend upon tube dimensions plus solvent mobility, polarity,
and surface tension.27,28 From the preceding ndings, dierent
non-solvents can produce dierent density values for the same
sample, hampering in such a way their characterization.
Another issue that complicates the use of non-solvent displa-
cing uids can be envisaged from published results. Asphaltene
samples have been determined to swell when exposed to organic
solvents.19 This eect is similar to coal swelling induced by
3665 dx.doi.org/10.1021/ef200780d |Energy Fuels 2011, 25, 36633670
Energy & Fuels
Figure 2. Solvent swelling of nC7-precipitated asphaltenes. Asphal-
tenes were isolated from virgin and oxidized (48 h under air bubbling)
Cerro Negro heavy petroleum 550 C+ vacuum residue. hf and ho are the
nal (solvent equilibrated) and initial asphaltene packed height, respec-
tively. Swelling details are presented elsewhere.19
dierent organic solvents or solvent mixtures.29
33 Liquids
contacting solid asphaltenes exert osmotic pressure that pro-
motes solvent uptaking until this eect is balanced by the
restoring elastic forces of the network. Solvent swelling of
asphaltenes isolated from vacuum residua asphaltenes is pre-
sented in Figure 2. Dramatic volumetric changes are observed to
occur after an equilibration period of 24 h. These asphaltenes
were observed to almost double its volume (expansion to about
100% additional volume) when an apolar solvent, such as nC7, is
the material contacting the sample. To the best of our knowledge,
this phenomenon has not been studied further since the pub-
lication of the paper.19 No information about the kinetics of
asphaltene swelling is available at present. Densities using nC7 as
displacing uid are routinely determined within 1 h after the
samples contact the solvent and are thermally equilibrated.1,4
Occurrence of volume expansion during density measurement
cannot be veried or discarded unless kinetics of volume expan-
sion are determined. At present, swelling eects on determined
sample densities are unknown because volumetric changes
during density measurement have not been studied.
All of these reasons justify the search for methods for density
determination less susceptible to secondary eects. The con-
ceived approach validated here relies on the use of solution
pycnometry.
3.2. Validation of Solution Pycnometry. Solution pycnome-
try must address the feasibility of volume expansion/contraction
from mixing of analytes with the chosen solvent. Solution ideality
must be guaranteed; i.e., volumes of mixtures should be additive.
This presumption is reasonably achieved if the solvent polarity is
similar to the sample polarity. This follows the widely accepted
principle of like dissolves like. Toluene is conceived as a good
candidate fulfilling the desired properties because (i) it displays
similar polarity to oil samples (the dielectric constant for toluene34 is
2.4 and within the range of 2.2
2.6 for oils35), (ii) it is a good
solvent for petroleum components, even solids, such as
asphaltenes,36 (iii) its boiling point (BP of 110.61 C at 1 atm) is
reasonably high for decreasing evaporation drawbacks during
pycnometry determinations,21 and (iv) water solubility in toluene
is very low (about 330 ppm),21 in this way, avoiding humidity
problems by solvent evaporation during pycnometry determination.
3666
ARTICLE
Figure 3. Correlation between known densities for reference materials
and determined values via toluene pycnometry. Analyzed materials are
described in Table 1. Outlayers detected in panel A were deleted, and a
better correlation is presented in panel B. Analyte group-type sets are
illustrated in panel B.
Validation of toluene solution pycnometry was initially ver-
ied by comparing values determined for selected known re-
ference materials. Figure 3 presents the results achieved. Solution
pycnometry with the toluene solvent provides density values that
match those determined for most analyzed materials. Interest-
ingly, most determined polar compound densities are observed
to match, which was not expected a priori. However, three solids
were observed to deviate, i.e., pyrene, uorene, and acridine. The
widespread deviation of the later is particularly noticeable, which
is expectable for polar compounds dissolved in an apolar solvent.
However, no explanations can be forwarded at present for the
behavior of the two apolar polyaromatics, i.e., uorene and
pyrene, whose solution density was determined to be lower than
reported (Table 1). Available evidence points toward an opposite
trend; i.e., their solution density should be larger instead of lower
than reported, on the basis of the following premise. Strong
intermolecular packing for these two solids is expected to occur
because they do not have alkyl substitutions. A rich alkyl
periphery has been evidenced to disrupt molecular packing,
facilitating solubilization phenomena.37 At present, it is speculated
that tight molecular packing of these unsubstituted aromatics
results in compact, lower volume entities that are not relaxed in
toluene. From the preceding, because density is calculated from
dx.doi.org/10.1021/ef200780d |Energy Fuels 2011, 25, 36633670
Energy & Fuels
the ratio of mass/volume, with volume being lower, it should result
in larger determined density values. These previous ndings raise
concerns for the samples of interest in the present study, i.e., solids,
such as asphaltenes. To better understand if toluene pycnometry
for solid asphaltenes is reliable, two experiments were carried out
as described in the ensuing paragraphs.
First, the absence of volumetric changes when mixing asphal-
tenes and toluene was veried. Three asphaltene toluene solutions
were prepared, spanning the range from 1.0 to 1.8 g in about 11 mL.
This concentration range covers the routine determination of
asphaltene densities, implying about 1.5 g/test (see the Experi-
mental Section). Results presented in Figure 4 suggest that
mixtures of asphaltenes and toluene in these proportions follow
mixture ideality; i.e., no volumetric changes were determined after
mixing. Ideal mixing of the studied petroleum asphaltenes with
toluene is believed to happen because asphaltene molecules are
surrounded by abundant alkyl moieties that preclude their extended
intermolecular interactions and the formation of large solid aggre-
gates dicult to dissolve. Typical Athabasca asphaltenes on average
contain 43 carbon atoms/100 carbons,38 suggesting that more than
half of these molecules bear paranic substituents that preclude the
formation of large solid aggregates. However, it must be said that
these substituent eects are not expected to avoid the formation of
nanosized aggregates commonly reported in the literature.39,40
A second proof for asphaltene ideal mixing was carried out by
experimentally determining the density of separated maltenes/
asphaltenes via toluene pycnometry. The density for the starting
feedstock (ATVR, i.e., Athabasca vacuum residue) was compared
to the density calculated from the separated deasphalting frac-
tions using nC5 and nC7 solvents, considering their massic
abundances (mass fractions, F). Results determined at 15.6 C
are presented in the following expressions:
ATVR 1:0554 g=mL C7 asphaltene
 FC7 asphaltene C7 maltene
 FC7 maltene
1:1801  0:1765 1:0341  0:8235
1:0598
ATVR 1:0554 g=mL C5 asphaltene
 FC5 asphaltene C5 maltene
 FC5 maltene
1:1825  0:2250 1:0196  0:7750
1:0563
From the preceding, calculated densities agree with the deter-
mined density for the whole Athabasca residue with an absolute
maximum deviation of 0.005 g/mL. This indicates that (i)
maltene/asphaltene densities are additive and (ii) toluene-
determined densities are reasonably representative and accurate.
Mixing ideality veried with the two experiments discussed
before indicates that the density for the samples of interest, i.e.,
asphaltenes and vacuum residua, can be determined reliably via
toluene solution pycnometry. It is presumed that the presence of
small quantities of insoluble materials, such as waxes or coke,
does not aect these measurements, provided that they are
quantitatively transferred into the glass pycnometers by thorough
rinsing of the sample containers.
Repeatability for any analytical methodology is always a matter
of concern. For toluene solution pycnometry, this parameter was
evaluated with three oil distillates plus n-heptane and o-xylene as
ARTICLE
Figure 4. Additivity verication of asphaltene/toluene solution volumes.
An industrial C5-precipitated asphaltene from Athabasca vacuum residue
(average density of 1.1424 at 15.6 C) was studied.
analytes. Determinations were carried out with three dierent
pycnometers, running at least three replicas in each case. Results
indicated (not shown in this paper) that variations were observed
in the third or fourth decimal positions. The worst-case scenario,
i.e., errors aecting the third position ((0.001 g/mL), translates
into a repeatability of (0.15 API gravity values. In addition,
analysis repeatability was evaluated with replicated analysis of
nC5-deasphalted Athabasca 550 C+ residue and its correspond-
ing steam catalytic cracking products. The nonvolatile fractions
separated after processing within a hot separator device are the
samples included in Figure 5. Reasonable API repeatabilities are
determined for the processed samples, with standard deviations
(SDs) spanning the 0.01
0.11 range. Only the feedstock was
observed to produce a larger variability (SD of 0.18). The
precisions found are deemed appropriate for process monitoring
purposes. The development of the present methodology was
undertaken mainly for handling cumbersome residual samples,
such as the viscous residua discussed herein.
3.3. Applications of Toluene Pycnometry to Maltene/
Asphaltene Samples Separated from Vacuum Residua. Solid
asphaltene and maltene fractions (DAO) derived from vacuum
residua are among the most difficult samples for density deter-
mination. Air bubbles removal from solids is a frequent problem
affecting measurements. The viscous and sticky nature of
residual DAO fractions is another problem. Three sets of
samples selected from these hydrocarbon types were studied
in this section to illustrate the application of toluene glass
pycnometry. The sets comprised: (1) one virgin Athabasca
vacuum residue (ATVR) and its nC5 and nC7 DAO/asphal-
tene fractions, (2) nC5 and nC7 asphaltenes isolated from
ATVR visbroken residua produced under varying severities, and
(3) nC7 DAO/asphaltene fractions isolated from an ATVR,
determined at different temperatures.
Figure 6 presents the density values determined for the rst two
sets of studied samples. Mild thermal cracking (visbreaking14)
was involved in these studies. Determined density values at
15.6 C for the whole residue fell in between its asphaltene and
maltene fractions. In preceding paragraphs, calculations were
made showing that these density values are additive. It is worth
noting that virgin C7 maltenes are slightly denser that C5
maltenes, and unexpectedly, virgin C5 and C7 asphaltenes
showed similar density values. Another interesting nding from
3667 dx.doi.org/10.1021/ef200780d |Energy Fuels 2011, 25, 36633670
Energy & Fuels
Figure 5. API gravity replicate determinations (n g 3) for the feedstock
and topped heavy bottoms derived from steam catalytic cracking of
deasphalted Athabasca 550 C+ residue. The tie line (SD) is appended
only as a visual aid.
this gure is that visbroken C7 asphaltenes are always denser that
visbroken C5 asphaltenes, suggesting that the co-precipitated
resins lower the density values for the later. One nal interesting
aspect shown in this gure is the value of visbroken asphaltenes
isolated from a product obtained near instability conditions, i.e., a
P value near 1.1 [visbreaking conversion of 28.5% (w/w)14].
Densities around 1.30 g/mL are determined for these asphaltenes,
which resemble typical density values for coals.2,12,13,26 Packed
structures resembling typical polyaromatic hydrocarbons are
suggested from the determined densities (for example, pyrene
density is 1.274 g/mL, and benzo[a]pyrene is 1.351 g/mL). The
discussed results suggest that dense visbroken asphaltenes can be
better represented by condensed molecular architectures de-
scribed as like your hand based in the combined picture
obtained from several characterization techniques.41 These con-
densed and dense materials are also described as island types42
and have been identied as the most troublesome fractions during
oil production,1,17 showing high aromaticity1 and possessing low
H/C atomic ratios and large condensed aromatic ring systems, as
indicated by simulation.4
Results presented in Figure 6 for visbroken asphaltenes
compared to virgin materials further indicate that thermal
cracking induces an increase in density values for the asphaltene
fractions as a function of visbreaking severity. It appears that a
plateau is reached after thermal cracking proceeds beyond
conversions of about 23 wt %. The most important presumed
reaction occurring in this process is cracking of alkyl appendages
(pendants) from aromatic cores43 and/or weak bond scission
(for example, sulde and disulde bridges).44,45 Alkyl appen-
dages are rich in hydrogen and show density values typical of
small alkane distributions centered at about C4
C12, i.e, about
0.75
0.80 g/mL. Their release from the heavy products can
rationalize the observed increase in density for the remaining
products from visbreaking.
Temperature changes can bring severe density changes to
vacuum residua, as recently published for Athabasca 500 C+
vacuum residue.46 Densities spanning from about 1.01 g/mL at
100 C to 0.88 g/mL at 350 C are presented therein. In the
present study, density values for nC7 maltene/asphaltene
fractions isolated from the Athabasca vacuum residue were
determined to assess the contribution of these two components
to the overall density of Athabasca vacuum residue. The
temperature range for these determinations was restricted to
3668
ARTICLE
Figure 6. Density of nC7 Athabasca vacuum residue and its isolated
virgin and visbroken maltenes/asphaltenes.
the interval within which toluene can be used as a convenient
solvent that does not disrupt the measurements by the produc-
tion of bubbles, i.e., 10
70 C. Higher temperatures are
expected to induce bubbling within the sample solutions
(toluene boils at 110.6 C/1 atm21). Figure 7 presents the
results achieved. The ndings indicate that asphaltenes dis-
played an approximated constant density of 1.170 ( 0.007 g/
mL within the evaluated temperature range. On the other hand,
the DAO fraction showed a steady decrease of about 0.025 g/
mL for the spanned 60 C temperature interval tested. From
these results, it seems that the important changes in density are
brought by the liquid components of the residue, at least within
the temperature range for these measurements. Within the
10
70 C temperature range, asphaltenes are solids and not
prone to noticeable density changes. If an attempt was made to
extrapolate asphaltene density determined at one of the above
set temperature values and then to use tables to calculate
densities at other temperatures, this experimentally determined
constancy is not veried by extrapolation because the tables
were developed for liquid samples.47 One question that remains
open is what happens if the temperature is increase above
205 C, where Athabasca asphaltenes reportedly behave as
liquids.7 Glass pycnometry with higher boiling solvents (for
example, xylene and tetraline of ca. 140 and 207 C, re-
spectively) should be used. Eventually, another technique
instead of glass pycnometry must be followed to answer this
question, with gas (helium) pycnometry being a suitable
option.
3.4. Solution Pycnometry with Different Organic Solvents.
The present study described toluene solution pycnometry of
residual fractions, including isolated asphaltenes. From recent
papers39,40 and considering a deemed high experimental con-
centration of asphaltenes in solution (about 15 wt/vol), aggre-
gates are believed to better describe the mixture state; i.e.,
densities are being determined for dispersed materials instead
of true dissolved substances. Dispersibility effects on determined
densities were investigated by preparing asphaltene solutions in
three different good solvents: toluene (chosen for the present
study), CHCl3, and THF. In addition, displacement with n-
heptane was compared for the set of studied Athabasca virgin
and visbroken asphaltenes. Achieved results are presented in
Figure 8.
Figure 8 indicates that determined density values agree for the
three tested good solvents. However, values determined with
dx.doi.org/10.1021/ef200780d |Energy Fuels 2011, 25, 36633670
Energy & Fuels
Figure 7. Density of nC7 asphaltenes/maltenes isolated from ATVR, as
a function of the temperature.
Figure 8. Density of C7 virgin and visbroken Athabasca residue
asphaltenes determined by solution or displacement pycnometry. Solu-
tions were prepared with toluene, THF, and CHCl3 solvents. Displace-
ment pycnometry was carried out with n-heptane. Replicated analysis
was carried out only with the toluene solvent.
n-heptane diered by approximately a factor of 0.96. The later
nding conrmed previous observations made with asphaltenes
isolated from other crude oils instead of Athabasca bitumen
(see the rst section of the Results and Discussion); i.e.,
dierent solvent displacers provide dierent density values.
Restricted access to the porous space of the solids by dierent
solvent displacers is probably the main cause; however, other
interactions discussed above can also play dierent roles.2,12,26
28
The fact that asphaltene dispersions in three dierent good
solvents provided the same density values is considered as
preliminary proof that fundamental asphaltene units are being
determined in these experiments. An analogy can be established
with helium in gas pycnometry; i.e., solution pycnometry is
believed to provide the most representative value of heavy, polar
oil components. Further research should be carried out to fully
understand these aspects.
3.5. Application of Toluene Pycnometry To Process Reaction
Monitoring. Toluene-based glass pycnometry was conceived for
handling cumbersome samples, such as asphaltenes and sticky
vacuum residua. However, the possibility of running several samples
simultaneously opens the feasibility of using it for routine monitor-
ing of samples derived from upgrading studies. One example
presented in Table 2 illustrates this possibility. Upgrading a
wide Athabasca distillate spanning from 250 to 516 C is
described, with the aim being to decrease viscosity to levels
that allow us to use the products as diluents for transportation
3669
ARTICLE
Table 2. Steam Catalytic Cracking of a 250
516 C Atha-
basca Distillate Using an Ultradispersed Catalyst Formulation
conversion at 350 C+ MCR viscosity at
sample (%, w/w) (%, w/w) API (deg) 25 C (cP)
feed 0.0 0.16 16.4 216
1 23.1 1.59 18.9 36.2
2 29.5 2.24 19.8 17.8
3 36.0 3.30 19.3 15.5
of diluted bitumen. Multimetallic ultradispersed catalysts for
steam catalytic cracking were used in these experiments.48
Conversion (as defined in eq 3) is calculated in this case as
the appearance of atmospheric distillates under a set limit of
350 C. It is noticed how API gravity determination was able to
detect the onset of product degradation that occurred when
severity reached a conversion of 36 wt %. Density reversal has
also been reported during high-severity thermal processing of
whole bitumen.49 In the present example, the conversion level
at which API reversal was determined corresponds to a MCR
content of 3.3 wt %, and no practical viscosity gains were
achieved from these severity levels. The example illustrates how
API (density) can be selected as another of the feasible
parameters for characterizing oil fractions during upgrading
processing.
4. CONCLUSION
Pycnometry of toluene sample solutions was studied and
demonstrated as a feasible, simple, and reliable technique,
applicable to highly viscous or solid samples, such as vacuum
residua and asphaltenes. Reported API gravities were found
reliable to (0.15 API; i.e., densities are aected to the third
decimal position. Density was determined to be an additive
parameter for heavy bitumen fractions, such as asphaltenes plus
maltenes. Athabasca vacuum residua nC7 asphaltene was deter-
mined to display an approximate constant density within the
10
70 C range, while its corresponding maltenes showed a
decrease of 0.025 g/mL in this temperature interval. Mild
thermal cracking (visbreaking) was determined to increase
Athabasca visbroken asphaltene densities to levels as high as
those displayed by coals (1.3 g/mL). Condensed aromatic
architectures account for these density ranges better. Solution
pycnometry is set up for routine analysis, illustrated with one
example describing the catalytic steam cracking of one Athabasca
distillate.
AUTHOR INFORMATION
Corresponding Author
*Telephone: 1-403-210-9707. E-mail: lcarbogn@ucalgary.ca.
ACKNOWLEDGMENT
The authors acknowledge funding from the Alberta Ingenuity
Centre for In Situ Energy (AICISE) and the facilities provided by
the Schulich School of Engineering, University of Calgary,
Canada. Manuel F. Gonzalez is thanked for his earlier involve-
ment in this research. Dr. Estrella Rogel from Chevron-ETC is
acknowledged for helpful discussions. Funding derived from
PDVSA-Intevep 1990
1995 projects managed by Drs. Orlando
Rivas and Alejandro Izquierdo is acknowledged for analysis of
dx.doi.org/10.1021/ef200780d |Energy Fuels 2011, 25, 36633670
Energy & Fuels
Venezuelan asphaltenes. Drs. Charles Bardon and Emmanuel
Behar from IFP-France provided helium pycnometry analyses.
Dr. A. Hassan is thanked for MCR analysis. Mariana Trujillo and
Pablo Gonzalez are acknowledged for routine pycnometry
analysis. Members of the pilot-plant facilities of the Schulich
School of Engineering are acknowledged for providing studied
Athabasca samples.
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