336 Energy & Fuels 1999, 13, 336-339

Analytical Considerations Related to Asphaltenes and

Waxes in the Same Crudes
B. J. Fuhr* and L. R. Holloway

Alberta Research Council, Edmonton, Alberta, Canada T6N 1E4

A. Hammami

D.B. Robinson Research Limited, Edmonton, Alberta, Canada T6N 1E5

Received September 30, 1998. Revised Manuscript Received January 11, 1999

Increasingly waxy crudes containing significant quantities of asphaltenes require characteriza-

tion, and established methods for separation of the waxes and asphaltenes are often not applicable.
An analytical scheme is described employing only one solvent, methylethyl ketone, to separate
asphaltenes and waxes, rather than an n-alkane and a ketone. The method consists of an
asphaltenes fractionation by filtration at 50 °C, followed by wax recovery by cooling to a specified
temperature (dependent upon the user’s needs) and filtration. The carbon number distribution
of the wax fraction may be determined by high-temperature gas chromatography, and the soluble
oil (minus asphaltenes and wax) can be further characterized by liquid chromatography and mass
spectrometry.

Introduction In the course of understanding the pour-point depres-

Asphaltene and wax deposition can cause problems
in crude oil production, transportation, and processing.
To develop remedial action to these problems and to
formulate predictive tools for simulating the deposition,
analytical protocols are required to supply the data.
Analytical methods for separating asphaltenes from
heavy crudes1 and waxes from waxy crudes2 have been
available for some time. When asphaltenes and waxes
coexist in and/or coprecipitate from the same crude in
relatively large amounts, analytical separation problems
can result. This often leads to waxy asphaltenes or black
waxes.
The waxy asphaltenes problem was noted by Alex et
al.3 in attempting a detailed characterization of wax
deposits. The solution in that work was to employ a
modification of the UOP method to first remove the
asphaltenes and polars as a group and then to separate
the wax from the remaining oil by precipitation from
acetone at -17 °C. The carbon number distribution of
the wax was determined using supercritical fluid chro-
matography, and the remaining oil was analyzed by
column chromatography and gas chromatography/mass
spectrometry (GC/MS). Even though the asphaltenes
and polars could not be separately quantitated by this
technique, the remaining data from this protocol was
successfully employed in a wax deposition model for
North Sea waxy crudes.
(1) Syncrude Analytical Methods for Oil Sand and Bitumen Process-
ing; Bulmer, J. T.; Starr, J., Eds.; Syncrude Canada Ltd.: 1979; pp
121-124.
(2) Paraffin Wax Content of Petroleum Oils and Asphalts; UOP
Method 46-64; Universal Oil Products Co.: Des Plaines, IL, 1964.
(3) Alex, R. F.; Fuhr, B. J.; Rawluk, M.; Kalra, H. Prepr. Am. Chem.
Soc., Div. Pet. Chem. 1991, 237-246.
sion mechanism of crudes, Irani et al.4 and Schuster and
Irani5 developed a method for isolating waxes. This
procedure was a modification of ASTM D-721,6 whereby
the samples were diluted with methylethyl ketone
(MEK), heated to 65 °C and filtered to remove insolubles
(asphaltenes), then cooled to -18 °C and filtered to
recover the wax. Analyses of the insolubles, waxes, and
oils by high-performance liquid chromatography (HPLC)
were also carried out during the course of this study,
which determined that asphaltenes could play a role in
the depression of the pour point.
The objective of the current work was to tailor the
analytical separation of asphaltenes, wax, and soluble
oil fractions from crude residue cuts, such that the
required characterizations of the waxes and soluble oils
could be easily carried out. Wax analysis usually
required a n-paraffin carbon distribution to the highest
attainable carbon numbers.
Experimental Section
The asphaltene/wax separation employed was a modification
of that described by Irani et al.4 and shown in Figure 1. It
consists of adding MEK to the sample, in a 10:1 (w/v) ratio,
heating to 50 °C and filtering to remove the hot MEK
insolubles (or asphaltenes), cooling to an appropriate temper-
ature, and filtering isothermally to recover the wax.
Analysis of the wax was carried out by high-temperature
gas chromatography (HTGC). A Hewlett-Packard 5890 equipped
with flame ionization detector was employed. The column was
(4) Irani, C. A.; Schuster, D. S. Prepr. Pap.sAm. Chem. Soc., Div.
Fuel Chem. 1985, 30 (1), 158-168.
(5) Schuster, D. S.; Irani, C. A. Prepr. Pap.sAm. Chem. Soc., Div.
Fuel Chem. 1985, 30 (1), 169-177.
(6) Oil Content of Petroleum Waxes; ASTM D721; American Society
for Testing and Materials: Philadelphia, PA, 1996.

10.1021/ef980205h CCC: $18.00 © 1999 American Chemical Society

Published on Web 02/18/1999
Asphaltenes and Waxes
Figure 1. Separation scheme for asphaltenes and wax from
crude residue.
a 15 m × 530 µm DB-1 of 0.1 µm film thickness. On-column
injection was used with a helium flow rate of 10 mL/min and
a temperature program of 35-450 °C at 10°/min.
A component-type analysis (saturates, aromatics, polars, or
SAP) of the soluble oil was carried out using alumina column
chromatography. This method is a modification of that de-
scribed in Alex et al.3 The column was 65 cm × 0.9 cm i.d.
packed with alumina activated at 400 °C for 20 h. The
respective eluents consisted of 100 mL of n-pentane for
saturates, 150 mL of toluene/pentane (70/30 v/v ratio) for
aromatics, and 100 mL of methylene chloride/methanol (50/
50 v/v ratio) for polars.
Results and Discussion
Waxy Crudes without Asphaltenes. Waxy crudes
without asphaltenes were first investigated in order to
simplify method development. The MEK wax separation
method from Figure 1 was modified for application to
residue cuts from crudes containing no asphaltenes.
Basically, the filtering step after heating to 50 °C, to
Figure 2. HTGC chromatograms of >350 °C crude residue and its 25 °C wax fraction.
Energy & Fuels, Vol. 13, No. 2, 1999 337
produce the hot solvent insolubles, was omitted. In this
case, a >350 °C residue cut from such a crude dissolved
completely at 50 °C, which was deemed a suitable
temperature to begin the separation. Lowering the
temperature of this very waxy crude to 25 °C resulted
in significant wax precipitation. HTGC analyses are
shown in Figure 2 for the original residue as well as for
the wax. The whole residue begins to elute at about C21,
which is expected for a >350 °C cut, and contains a very
broad hump, presumably consisting of branched and
cyclic paraffins as well as aromatics. Superimposed on
this hump is the pattern of n-paraffins, making it
difficult to obtain a quantifiable carbon number distri-
bution. The 25 °C wax, on the other hand, as seen from
Figure 2, produced a noticeably different chromatogram.
This trace is almost devoid of the hump, making it
relatively easy to quantify the corresponding n-paraffins
up to C70. Of course, because of the relatively high wax
precipitation temperature, the paraffins between C21
and C30 are missing.
The same separation scheme was applied to the >340
°C residue cut from another crude which also contained
no asphaltenes. This time waxes were obtained at sever-
al different temperatures from 20 to -15 °C; the amount
of wax obtained in each case is indicated in Table 1,
along with the maximum carbon number and the distri-
bution widths. The latter quantities are also shown for
reference for the whole >340 °C residue. Not surpris-
ingly, the amount of wax increases substantially and
the distribution shifts to lower carbon numbers as the
temperature decreases; this was also indicated by Schu-
ster and Irani.5 The HTGC chromatograms of the high-
est and lowest temperature waxes are shown in Figure
3. Several features are worth noting. First of all, the 20
°C wax, even though it produces the least amount be-
cause it does not contain the C21-C30 peaks, is the clean-
338 Energy & Fuels, Vol. 13, No. 2, 1999
Figure 3. HTGC chromatograms of 20 and -15 °C wax fractions of >340 °C crude residue.
Table 1. Amount of Wax Precipitated as a Function of
Temperature
carbon no. carbon no.
temp (°C) wt % wax max range
whole >340 °C residue 23 20-55
20 3.4 31 23-70
10 12.4 26 21-64
0 14.6 25 21-58
-15 36.3 24 21-46
est chromatogram with virtually no hump and showing
quantifiable carbon numbers up to C70. Some resolution
of i-paraffin peaks is also seen in the C35 area. Second,
the -15 °C wax has a relatively larger hump and shows
much less detail in the high carbon number region, even
though it does contain the C21-C30 paraffins.
In summary, this portion of the study demonstrated
that cooling of MEK mixtures of waxy crude residues
from 50 °C will produce a filterable and recoverable wax.
It is assumed that this temperature will be sufficient
to dissolve all the wax; if it is not, it should be increased.
The temperature to which the mixture is cooled should
be determined by what kind of wax characterization is
required by the user of the data. In other words cooling
to a low temperature, -18 °C, will produce a wax value
which will correspond to the UOP standard wax value
and contain significant i-paraffins, naphthenes, and
aromatics, as well as the C21-C30 n-paraffins. If, how-
ever, characterization of the highest carbon number
carbons in the wax is desired, the precipitation temper-
ature should be much higher, ambient temperature or
slightly less. In this way, a much smaller amount of wax
is recovered but naphthenes, aromatics, and the lower
n-paraffins (C21-C30) are excluded, which allows a
detailed characterization of the n-paraffins to the high-
est values, that portion of the wax often considered the
more troublesome. Some i-paraffins are usually precipi-
Fuhr et al.
Table 2. Comparison of SAP Analysis (as wt % of soluble
oil) after Different Asphaltene/Wax Separation Schemes
omission of hot MEK
insolubles step as in Figure 1
saturates 61 60
aromatics 27 26
polars 12 14
tated along with the n-paraffins and could be quanti-
tated by HTGC as well.
Waxy Crudes with Asphaltenes. As stated previ-
ously, the scheme used for separation of asphaltenes and
wax is shown in Figure 1. Dissolution of the wax is
usually ensured at 50 °C, yet allows the hot MEK
insolubles (or asphaltenes) to be filtered. Two experi-
ments were carried out with a >270 °C residue cut from
a waxy crude containing asphaltenes. The first was as
already outlined in Figure 1; the second omitted the
filtration and determination of the hot solvent insol-
ubles. In both cases, the wax or wax/asphaltene copre-
cipitate was obtained at -10 °C. The purpose was to
demonstrate that the omission of that step would actu-
ally result in coprecipitation of asphaltenes and waxes.
In the first case, the separately determined asphaltenes
and wax values were 11% and 41%, respectively, for a
combined total of 52% (of the original residue). In the
second instance, the coprecipitate amount was 48%,
close to the separately determined values.
Table 2 provides data on the component-type (or SAP)
analysis of the soluble oils of the >270 °C residue
obtained by the two experiments described previously.
The results show that the soluble oils are basically the
same, indicating that the asphaltenes which are filtered
out in the normal separation will end up in the waxy
fraction if not removed first. Although not shown here,
detailed characterization of the saturates and aromatics
fractions of the soluble oil by GC/MS may be carried
Asphaltenes and Waxes Energy & Fuels, Vol. 13, No. 2, 1999 339

Figure 4. HTGC chromatograms of -10 °C wax and hot solvent‚insoluble fractions of >270 °C crude residue.

Table 3. Comparison of Solvent Insolubles

out in order to provide data on asphaltene and wax
stability and deposition potential. solvent temp (°C) wt %
The HTGC chromatogram of the -10 °C wax dis- n-pentane ambient 20.9
cussed previously is shown in Figure 4. A reasonably n-hexane 50 14.4
MEK 50 13.4
clean chromatogram with a small hump and some indi-
cation of i-paraffins around C30 is seen; a good n-paraffin tion, its wax solubilization potential is too high for wax
distribution may easily be determined from such a determination.
chromatogram. The corresponding chromatogram of the It is not the authors’ intention to suggest here that
hot solvent insolubles or asphaltenes shown in Figure correlations should be made between asphaltene defini-
4 suggests a small amount of wax coprecipitated with tions. It should be stressed, however, that anytime an
the asphaltenes, even after heating to 50 °C. This trace asphaltene value is given, its operational definition
wax was estimated based on the GC area counts to be should be stated.
5% of the asphaltenes fraction. This behavior is similar Conclusions
to that found by Schuster and Irani,5 who stated that
A method has been adapted for the analytical separa-
saturates and asphaltenes associate with one another
tion of asphaltenes and waxes when they coexist in the
and do not totally separate during bulk deasphaltening.
same crudes. The method employs one solvent, MEK,
Comparison of Deasphaltening Solvents. The
rather than an n-alkane for asphaltenes and a ketone
definition of asphaltenes is an operational one, and as
for wax. The MEK, when added to the crude and heated
such it depends on the conditions (solvent and temper-
to 50 °C, solubilizes the wax but not the asphaltenes
ature) employed in their precipitation.7 In the current
(or hot MEK insolubles). The amount of these asphalt-
work, the definition is MEK solvent and 50 °C; in Irani
enes, as determined by filtration at 50 °C, is similar to
et al.4 it was MEK and 65.5 °C. A more common
that obtained using hot n-hexane. By merely lowering
definition of asphaltenes is n-pentane and ambient
the temperature of the same mixture to an appropriate
temperature;1 hot n-hexane has also been employed,
value, precipitated wax may be recovered by filtration
particularly for determining small amounts of asphalt-
and subjected to HTGC analysis for n-paraffin distribu-
enes in waxy crudes. Therefore, a comparison was made
tion. The wax precipitation temperature will depend on
among solvents and conditions using a residue sample
the type of data required. For example, a temperature
originating from a heavy oil, which contains no waxy
of 25 °C will provide good information about the highest
components; the results are shown in Table 3. It can be
carbon number range; conversely, -18 °C will provide
seen that the hot MEK definition gives a significantly
a %wax value closer to the UOP value but yield low
lower value than the n-pentane insolubles; however, it
resolution at the high carbon number end. The soluble
comes close to the hot n-hexane definition. While the
oil is available for analysis of component types (SAP),
latter solvent is also useful for asphaltenes determina-
with subsequent detailed characterization by GC/MS if
desired.
(7) Speight, J. G. The Chemistry and Technology of Petroleum;
Marcel Dekker: New York, 1980; pp 118-127. EF980205H