See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/239396280

Simple Techniques for Evaluation of Crude Oil Compatibility

Article  in  Petroleum Science and Technology · July 2004

DOI: 10.1081/LFT-120038695

CITATIONS READS
32 6,063

3 authors, including:

Frans G.A. van den Berg

Shell U.K. Limited
12 PUBLICATIONS   251 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Heavy oil and asphaltene solutions View project

All content following this page was uploaded by Frans G.A. van den Berg on 28 April 2016.

The user has requested enhancement of the downloaded file.

 SIMPLE TECHNIQUES FOR EVALUATION
OF CRUDE OIL COMPATIBILITY

W.E.M. Schermer, P.M.J. Melein and F.G.A. van den Berg

Shell Global Solutions International B.V., P.O. Box 38000

1030 BN Amsterdam, Netherlands

ABSTRACT

Blending crude oils or crudes and condensates of different origin may give rise to
deposit related problems due to incompatibility. Although the problem has been
recognized, there are as yet no standard methods for the determination and
quantification of crude oil compatibility. This study focused on the compatibility
of stock tank oils in storage depots and refineries.

Using blends of Arab Medium and Gippsland crude oils as a model system,
various simple techniques were investigated and compared with the results of the
in-house Shell stability test (the Po/FRmax test): microscopy, a modified Hot
Filtration Test, a modified ASTM spot test and a modified Shell Spot test. All
techniques (with the exception of the ASTM spot test) were capable of
identifying an unstable regime, but the onset of asphaltenes flocculation varied
with the experimental conditions. Sample pretreatment was found to be a
necessary prerequisite for obtaining meaningful data. The Shell Spot Test
appears to be a fast and simple method for monitoring crude oil compatibility in
the downstream business.

Published in Petroleum Science and Technology

Volume 22, Issue 7-8, 2004.
 INTRODUCTION

Several studies have shown that blending of different crude oils may lead to
precipitation of asphaltenes (Asomaning and Watkinson, 1999, Wiehe and
Kennedy, 2000, Van den Berg, Kapusta et al, 2002). This phenomenon, known
as crude oil incompatibility, causes significant problems in transportation and
refining. Practical experience suggests that this problem is restricted to blends of
crudes from very different origins or crude/condensate blends. However, the
problem of incompatibility appears to be rising, especially in those refineries
which are under pressure to widen their crude diet in an effort to improve the
present low margins.

Recognition of the problem of incompatibility has not yet led to a standard

method for the determination and quantification of crude oil incompatibility.
Various methods describing asphaltene stability and allowing prediction of
compatibility have been described in the literature. Incipient precipitation uses an
aromatic solvent and a non-solvent (e.g. heptane or hexadecane) to determine
asphaltene solubility numbers (Lewis et al, 1985, Wiehe and Kennedy, 2000).
Automated techniques to evaluate the stability of crudes and/or heavy oil streams
have recently been introduced (Vilhunen, 1999, Van den Berg, 2000, Stark,
Nguyen and Kramer, 2002).

A potentially different approach is to evaluate the geochemical origin of the

crudes (Van den Berg, Heijnis at al, 2002): crudes from similar origin are
expected to be compatible, whereas crudes from very different origin (e.g. a
heavy asphaltic crude with a light paraffinic crude) are expected to be
incompatible. However, prediction of crude compatibility in this way requires
considerable expertise.

The lack of a standardized method has hitherto prevented the introduction of

asphaltene stability data in crude oil assays. ASTM Subcommittee D.02.14 is
investigating the need for such a standard method and preparing an inventory of
suitable techniques. In the mean time, we perceived the need for a simple test
which could be carried out in the field (blending stations, refineries etc) to assess
potential incompatibility problems.

In this paper we use a potentially incompatible blend to investigate the

applicability of various test methods. Arab Medium (AraM) is a relatively
immature marine crude from Saudi Arabia. Gippsland (Gipp) is a mature
paraffinic crude oil from Australia. Blends of these two crudes show complex
behavior due to the presence of water droplets, waxy material and insolubles.
Researchers active in the field will recognize that asphaltene and wax deposition
phenomena can be significantly affected by the history of the samples. As part of
this study, we therefore investigated the effects of sample pretreatment, storage
time and temperature.

EXPERIMENTAL

Feedstocks
Relevant properties of the two crudes are shown in table 1.

Property Method Arab Medium Gippsland

Density at 15 °C, kg/l ASTM D1298 0.878 0.796
Viscosity at 40 ° C, mm2/s ASTM D445 10.9 2.75
Sulphur content, %w ASTM D2622 2.5 0.08
Nitrogen content, ppmw ASTM D4629 1300 89
Asphaltene content, %w IP 143 3.25 <0.05
Wax content, %w SMS 1769 5.0 14
Atmospheric residue, %w ASTM D2892 49.6 18.0
Table 1: Bulk properties of tank crudes

Sample pretreatment and blending procedures

Before blending, both crude oils were conditioned at 45 °C in an oven. Blends
were prepared by adding Gipp to AraM to avoid local instability. Blends were
stirred with a magnetic stirrer for 5 minutes before testing. Screening tests were
carried out with 0, 10, 20,40, 60, 80, 90 and 100 % Gipp. Additional blends were
prepared to investigate the onset of precipitation more closely.

Microscopy
An optical microscope (Orthoplan, Leitz), equipped with a digital image analyzer,
was used for visualization. A L25/035 objective (NPL Fluotar) resulted in a
magnification of 250x. The microscope contains two light sources: regular and
polarized light (to identify possible wax crystals).

Modified hot filtration test

A weighed amount of blend (10 g) was stirred at 60 °C before filtration through
the apparatus and procedure prescribed by ASTM D4870 at 60 °C.

Spot tests
ASTM D4740: A homogeneous sample (50 ml) of the blend is heated to 60 °C
for one hour. A drop of the mixture is then allowed to spread by absorption on a
filter paper. The test paper is dried at 60 °C for one hour and visually inspected
for the presence of a dark inner ring. The absence of a ring indicates that the
blend is compatible.
Shell Spot Test (SMS 2712): A homogeneous sample (5 ml) is diluted with 10 %
v hexadecane and stored at 60 °C for one hour . A drop of the mixture is then
allowed to spread by absorption on a filter paper. The spot formed is washed
with n-heptane, the test paper is dried and inspected for the presence of a dark
inner ring. The absence of a ring indicates that the blend is compatible.

Stability reserve (SMS 2715, Po/FRmax)

In this Shell method, the solubility of the crude oils (Po) and the required
solubility of the asphaltenes (FRmax) are measured by incipient precipitation
techniques (Lewis et al, 1985, Van den Berg, 2000). Po and FRmax are derived
by comparing the sample with known combinations of cetane (Po = 0) and 1-
methylnaphthalene (Po=100). A crude or blend is stable as long as Po is greater
than FRmax (Po/FRmax > 1). When the Po and the FRmax of two crudes are
known, the compatibility of each blend can be predicted .

RESULTS AND DISCUSSION

Sample pretreatment and blending

AraM is a clean crude which shows practically no visible particulates under the
microscope. Gipp, however, is quite dirty, containing water droplets, wax
crystals and other insolubles. It was not possible to discriminate between
flocculated asphaltenes and other contaminants. For this reason a number of
different pretreatment techniques were investigated at different temperatures.
The best results were obtained when using the following:
- pressure filtration at 1 bar nitrogen pressure
- a conditioning time of 1 hour in the pressure holder
- a double filter (Whatman nr 3 paper above a 0.5 μ FH isoprene Millipore filter)
- a temperature of 60 °C
This combination removed practically all the interfering contaminants while
leaving most of the wax in the crude.

Microscope investigations
Addition of warm, filtered Gipp to warm AraM led to a series of blends
containing increasing amounts of insoluble material. The fresh blends were
stirred for five minutes and a drop of each blend was immediately put on an
microscope slide (heated to 45 °C to avoid wax crystallization). Under these
conditions the blends with 80 % and 90% Gipp showed a strong increase in the
number of very fine particles, whereas the blend with 60 % Gipp did not. This
defined the incompatibility point at anywhere between 60 and 80 %w of Gipp.
However, a repeat of the same test after 7 days of storage at 45 °C showed that
the blend with 60 % Gippsland showed asphaltene flocculation as well. The
same tests were repeated after 14 and 28 days, but no further changes were
observed (see table 2).
Blend ratio (m/m) Day 1 Day 7 Day 14 Day 28
AraM/Gippsland
100/0 clean clean clean clean
90/10 clean clean clean clean
80/20 clean clean clean clean
60/40 clean clean clean clean
40/60 clean asphaltenes asphaltenes asphaltenes
80/20 asphaltenes asphaltenes asphaltenes asphaltenes
10/90 asphaltenes asphaltenes asphaltenes asphaltenes
0/100 clean clean clean clean
Table 2: Storage effects on blends of AraM/Gipp crude oils (NB: blends were
stored under nitrogen to avoid oxidation effects/evaporation)

Modified hot filtration test

The results of the filtration tests are shown below.

0.03
sediment, %m

0.02

0.01

0
0 20 40 60 80 100
% Gippsland, m/m

Figure 1: Sediment levels indicate onset of incompatibility

Figure 1 shows that the amount of sediments present in (unfiltered) AraM (0.024
%w) is diluted by adding the filtered Gipp. Above 70 %w Gipp the amount
increases again; the sediment increases between 70 and 75 %w of Gipp.
Spot test results
The results of the ASTM and Shell Spot Tests are shown in table 3. In the ASTM
test, incompatibility was very difficult to see (spots were too dark to discriminate
a ring). The Shell Spot Test gave much clearer spots which is likely due to the
additional heptane rinse step.
Blend ratio (m/m) ASTM spot test Shell Spot Test
AraM/Gipp number (ASTM rating)
100/0 1 Compatible (1)
80/20 1 Compatible (1)
60/40 1-2 ? Compatible (1-2)
40/60 1 Compatible (2)
30/70 not measured Incompatible (2-3)
25/75 not measured Incompatible (3)
20/80 1 Incompatible (3-4)
0 1 Compatible (1)
Table 3: Comparison of ASTM and Shell spot tests

Stability reserve
Results of the Po/FRmax measurements are shown in table 4. AraM has a Po of
44, a FRmax of 24 and a P-ratio of 1.84. This makes it a relatively stable crude.
The Po decreased steadily with increasing amounts of Gipp, whereas the FRmax
decreased only slightly. Unfortunately, the Po/FRmax test did not give
meaningful results for Gipp, due to the absence of asphaltenes. Therefore the Po
of Gipp was calculated using a correlation based on known solubility numbers of
other refinery streams. This resulted in a Po of 19.

Table 4 shows the measured and calculated stability data. In the calculations, the
Po were blended linearly on a volume basis. The FRmax of AraM (24) was used
in all calculations. In practice, however, the FRmax is not constant, but gradually
decreases with increasing % of Gipp. This appears to be a concentration effect.
Blend ratio Po FRmax P-ratio P-ratio
AraM/Gipp predicted
100/0 44 24 1.84 1.84
80/20 35 23 1.51 1.61
60/40 31 23 1.35 1.39
50/50 28 21 1.33 1.29
40/60 23 21 1.14 1.19
35/65 23 21 1.10 1.14
30/70 22 20 1.09 1.08
20/80 17 19 0.91 0.99
0/100 (19) - -
Table 4: Calculated and predicted stability data
Figure 2 shows the measured and calculated P-ratio for the AraM/Gipp blends.
According to the analyses, incompatibility starts to occur at 76 % v Gipp. This is
quite close to the predicted value of 80 %v.

1.90
1.70
1.50
Pratio
P ratio

1.30
Pratio calculated
1.10
0.90
0.70
0.50
0 20 40 60 80 100
Volume % Gippsland

Figure 2: Comparison of predicted and actual stability data

COMPARISON OF FIELD METHODS

The various test methods all identified the borderline of stability between 60 and
80 % Gipp. The microscope method was found to require a trained eye and the
results were easily obscured by the presence of wax crystals. The modified hot
filtration test has the drawback that the observed differences are small compared
to the reproducibility of the method. The ASTM spot test (originally developed
for fuel oils) did not show clear spots. For field applications the Shell Spot Test
therefore appeared to be the most promising technique. It requires only a small
volume (5 ml) and is fast and simple. It has the additional advantage that the
samples are first diluted with 10 % cetane, thus ensuring a margin of stability
reserve. This is especially useful in practice, where various circumstances
(imperfect blending, ageing effects, measurement errors) may result in small
shifts in blend stability. In order to facilitate application, the existent Shell Spot
Test Kit (originally developed for the bunker fuel market ) is being adapted for
crude oil purposes.
 CONCLUSIONS

Due to the inherently dirty nature of crude oils, definition of a suitable

pretreatment step is a prerequisite for any crude oil compatibility test.

Microscopy, filtration tests and the Shell spot test were all capable of defining
incompatibility in a model blend of Arab Medium and Gippsland. The exact start
of incompatibility varies between 60 and 80 %w, depending on the method used.

The Shell Spot Test appears to be a fast and simple method for monitoring crude
oil compatibility in the downstream business.

Long term storage may have an effect on the stability of crude oil blends.

REFERENCES

Asomaning, S and Stark, J.L., 2002. Paper presented at the 2002 AIChE Spring
Meeting, New Orleans, Louisiana, March 10-14, 2002.

Lewis, C.P.G., Johnson, E.K.,and Berryman, T.J., 1985. Paper presented at the
16th CIMAC Conference Oslo, June 1985.

Stark, J.L, Nguyen, J and Kremer, L.N. 2002. Oil &Gas J., March 18, 89-91.

Van den Berg, F.G.A., 2000, Paper presented at IASH 2000, Graz, Austria,
September 24-29, 2000.

Van den Berg, F.G.A, Kapusta, S.D, Ooms, A.C and Smith, A.J, 2002, paper 58b
AIChE Meeting New Orleans, Louisiana, March 10-14, 2002.

Van den Berg, F.G.A., Heijnis, R.M.A., Stamps, P.A. and Kramer, P.A., 2002,
paper 48f, AIChE Meeting New Orleans, Louisiana, March 10-14, 2002.

Vilhunen, J., 1999, Paper presented at the 3rd International Symposium on the
Thermodynamics of Heavy Oils and Asphaltenes, Houston, March 1999.

Wiehe, I and Kennedy, R.J. 2002, Energy & Fuels, 14, 56-59.

Acknowledgement
The authors are grateful for the stimulating ideas and discussions with numerous
colleagues in Shell Global Solutions. We like to thank P. Valentijn for his skilful
execution of the Po/FRmax tests. We also thank Shell Global Solutions for
permission to publish this paper.

View publication stats