SPE 161936

Workflow for Asphaltene Precipitation Assessment and Mitigation

Strategies
Honggang Zhou, Total E&P, Nicolas Passade-Boupat, Total Petrochemicals France, Marianna Rondon Gonzalez,
Total Petrochemicals France

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 11–14 November 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract
The prediction of the risk of asphaltene precipitation is an important topic in the petroleum industry. It usually requires
representative samples and measurements using specialized, high-pressure equipment, and may have to be performed on
many different fluids from various reservoirs. Of the many fast screening methods have been proposed, most of them only
take into account the hydrocarbon phase without any investigation on the actual asphaltenes in the crude, and may lead to
erroneous predictions.
This paper presents a universal approach of the risk of precipitation of asphaltenes.
A new experimental way to perform fast screening of asphaltene instability is proposed based on relevant solubility
properties of the asphaltene fractions. It is based on two major parameters: the live oil solvent properties (based on PVT
analyses) and the actual solubility of asphaltene fraction, through an easy characterization procedure that examines the
solubility of asphaltenes in heptane/toluene mixtures. In field development projects, this method, which can be performed on
dead oil samples, helps limit the investigation to fluids that present a real risk of asphaltene precipitation.
If a precipitation risk is stated, two paths are followed in order to estimate the risk level, and to prepare a mitigation strategy.
Additional tests, performed on pressurized representative samples or taking into account reorganization of asphaltenes from
different fluids, will help to define the severity of the risk. For mitigation, an advanced test set-up has been developed, which
facilitates evaluation of the efficiency of chemical additives to prevent plugging under flow conditions of fluids above the
asphaltene precipitation threshold. Depending on the crude oil, the severity of the precipitation conditions, and the nature of
the additive, the blocking of a capillary tube can be delayed or prevented.

Introduction
The understanding and the prediction of asphaltene precipitation are an important topic in petroleum industry. Reliable
evaluation of the asphaltene stability requires representative samples and measurement using special high pressure
equipments. Moreover, important development projects may involve many reservoirs with many different fluids. Even inside
of a connected reservoir, the quality of the oil and the asphaltene can vary through a large scale, and the investigation of each
fluid in their representative conditions become very expensive and often impossible. Fast screening methods are then
required to discard the low risk cases in order to concentrate the investigations on the high risk cases.

Many fast screening methods have been proposed so far. The De Boer’s diagram is one of the most useful [1], [2]. However,
it only takes into account the properties of the hydrocarbon phase without any investigation on the asphaltene fraction. Thus,
this method gives mostly pessimistic prediction of the risk of asphaltene precipitation. If many other screening methods have
been proposed, most of them have the same drawback, as they only take into account the composition of the hydrocarbon
phase and the concentration of asphaltenes without any investigation on the actual solubility class of asphaltenes in the crude.
Knowing the solubility class of the asphaltenes is one of the two most important properties in order to accurately predict the
risk linked with deposition of asphaltenes. The composition of the hydrocarbon phase gives insight on the solubilization
power of the oil, the other important property of the system. Only taking into account the percentage of asphaltenes, without
considering their solubility class, consider the asphaltene fraction in an irrelevant way, and it may lead to erroneous
predictions.
2 SPE 161936

In addition, the mechanisms of asphaltene precipitation are not always well understood. Thus, it is not uncommon to see
misdiagnosis when solid deposits are found: asphaltene deposition is diagnosed when it is simply mineral deposits or other
organic deposits containing evaporated oil residue; pressure effect is diagnosed while compatibility problem can occur;
asphaltene precipitation considered as impossible while it can occur through a tricky mechanism etc. Thus, an asphaltene
characterization method which can be used as a tool for diagnostics is very useful.

The method “ASIST” proposed by Buckley & al. [3], [4] takes into account implicitly the solubility class of the asphaltene
fraction and gives pretty good prediction of the asphaltene instability of the live oil using measurements performed on dead
oil samples. However, this method requires the use of a specific apparatus and does not measure explicitly the solubility class
of the asphaltenes fraction. Our approach is to use directly a relevant solubility property of the asphaltene fraction instead of
using complex models and chemical analyses for the understanding of the driving force of asphaltene precipitation and for
the risk evaluation. As will be explained latter in the experimental section, the method is based on the fact that the stability of
the asphaltene fraction in oil or in organic solvent depends strongly on the quality of the solvent (i.e. its composition) or of
the oil (i.e. mainly its density above the bubble pressure and its average molecular weight) and is almost independent of the
dilution. Consequently, it is difficult to describe the asphaltene stability in term of “solubility” which is expressed in weight
fraction or in mole fraction. The term of solubility class is more appropriate.

According to this solubility property, we propose an easy characterization method called ASCI rating (for Asphaltene
Solubility Class Index). The procedure for the determination of ASCI is described in the experimental section. This rating
method is applicable on an oil sample, on a residue of distillation as well as on a deposit sample. In the last case, the solid
sample needs to be re-dissolved in a small quantity of solvent prior to the ASCI rating. For asphaltene rich oils, the sample
can be diluted by toluene before measurement. Based on this rating method, a new and easy way to perform fast screening of
the asphaltene instability is proposed in this work. Using some PVT properties of the live-oil, this method leads us to limit
the investigation to the fluids which present a real risk of asphaltene precipitation. The asphaltene characterization can be
done using dead oil samples. Representative samples are required only for advanced investigation once the fluid is assessed
as risky from the point of view of asphaltene stability.

A second solubility property of the asphaltene fraction is important to be mentioned since it is important for the diagnostics
when a precipitate is discovered in a production line. In spite of the insensitivity to dilution of the asphaltene stability, when
the precipitation onset is reached, asphaltene precipitate progressively. This partial precipitation is not linked to the
“solubility” of the whole asphaltene fraction, but to the distribution of different asphaltenes with different solubility class
inside of the same oil. In addition, a strong interaction exists between the different asphaltenes species: even at low
concentration, some unstable asphaltenes can become stable because of the presence of stable asphaltenes. As a consequence,
when asphaltenes contained in a crude oil are fractionated by partial precipitation, the ASCI of the precipitated fraction
should be significantly lower than the initial ASCI of the oil. The importance of fractionation of asphaltenes with different
solubilities can be seen not only on deposition issues, but also on the behavior of oil / water interfaces [5] - [7].

These intriguing properties can be used to analyze the phase behaviors of the asphaltenes in order to make differences
between the asphaltenes enrichment by phase separation such as precipitation or liquid - liquid separation, and the enrichment
by other mechanisms such as segregation or gas striping. In the case of asphaltene enrichment by gas striping, the ASCI of
the oil should not be modified since there is no asphaltene fractionation. In the case of gravity segregation, a continuous shift
of ASCI can be observed versus depth and no difference should be observed on term of ASCI rating between the core extract
and the oil sample from the same depth. In the case of asphaltene precipitation, a strong difference should be observed
between the ASCI of the dissolved precipitate and the ASCI of the oil samples.

The following sections give an experimental description of how the measurement is performed, as well as examples on how it
can be practically used in order to assess either a deposition problem or to focus on the most relevant fluids for a field
development.

Experimental section: Determination of the Asphaltene Solubility Class Index (ASCI)

One of the specific characteristics of stability of asphaltenes is its strong sensitivity to the quality of the solvent and its very
low sensitivity to dilution. For example, if a given quantity of an asphaltene fraction flocculates in a given ratio of a mixture
of toluene and n-heptane, these asphaltene will still flocculate even if we dilute with 10 or 100 volumes of the same heptol
mixture. But if it is soluble in this mixture at a concentration of 0.1% wt, it will remain soluble in the same mixture at 1%wt.
On the other hand, only a very weak modification of the ratio toluene/n-heptane can modify in a spectacular way the
solubility of an asphaltene fraction. Flocculation can be induced by adding a few grams of n-heptane in one litre of toluene /
n-heptane mixture containing dissolved asphaltenes.
To describe the behaviour of such a petroleum fraction, it is not really convenient to use the word "solubility" which
generally indicates the maximum quantity of a component that can be dissolved in a solvent, and it is not really possible to
SPE 161936 3

link such a behaviour to traditional "solubility equilibrium" and "solubility constant", as the solubility parameter of the
solvent is a much better parameter than the concentration in solution. So, a more appropriate description of the ability of an
asphaltene fraction to remain soluble should be its solubility class. We can characterize the behaviour of an asphaltene
fraction by a kind of "Asphaltene Solubility Class Index" (ASCI).
To measure this index of an asphaltene fraction, we add a few drops of a crude oil, or a solution of asphaltenes, in standard
solvent mixtures as described in Table 1. The quantity of the oil, or asphaltene solution, added must be insignificant
comparing to the quantity of the standard solutions (usually <1% wt).
Table 1 Solvent mixtures for ASCI measurement

Solution n° n°0 n°1 n°2 … … n°18 n°19 n°20

Toluene 100%wt 95%wt 90%wt … … 10%wt 5%wt 0%wt
n-heptane 0%wt 5%wt 10%wt … … 90%wt 95%wt 100%wt
ASCI
0 1 2 … … 18 19 20
(n-heptane %/5)

These solutions are then stirred and stored at 50°C for about 48 hours before observation. If the asphaltene precipitation starts
in the pure toluene, the "asphaltene" fraction obtains an index equal to 0 (0% heptane). In case of the “asphaltene” fraction
precipitates only in pure n-heptane, it gets an index equal to 20 (100% heptanes). If the solution k shows a precipitate but the
asphaltene fraction is soluble in the solution k-1, it gets an index equal to k.
Contrary to other methods used to qualify solubilities of asphaltenes, the ASCI procedure, with long enough times and high
dilution ratio, tries to define a thermodynamic solubility, and to avoid kinetic effects.
From our experience, the concentration of asphaltenes in the oil has little incidence on the solubility class index measured
using this method as long as the minimal by-pass ratio (one oil mass for more than 20 masses of standard mixture) is
respected. For crude oils having a high level of sediment, a good way to detect the precipitation point, without being tricked
by the presence of these sediments, is to remember that the fraction of asphaltenes precipitated should increase when the level
of heptanes, i.e. the ASCI note of the solvent, increases.
Fig. 1 illustrate the insensitivity of the ASCI note, hence the asphaltene precipitation threshold, to dilution. An oil containing
about 3%wt of asphaltene as measured by standard ASTM method is diluted in toluene at three concentrations going from 2.5
%wt to 0.1%wt. It represents between about 750 ppm and 30 ppm of asphaltenes. The ASCI note of these model systems is
determined, as previously explained, by adding a few drops of the solutions to the heptol mixtures. Whatever the
concentration of asphaltene, precipitation is never seen for ASCI=12 (60% heptane), and is always seen for ASCI=13 (65%
heptane). It is also possible to see in Fig. 1 that the amount of precipitated asphaltene increases with the heptane/toluene ratio
going from ASCI=13 (65% Heptane) to ASCI=15 (75% Heptane).
This Total in-house method allows comparison between asphaltene fractions, independently of their solvent media. The
higher the ASCI, the more stable the asphaltene fraction, as it requires more precipitating solvent to induce phase separation.
For a given hydrocarbon solvent, the solubilization of an asphaltene fraction implies that this solvent allows the solubilization
of all the fractions having a higher solubility class index. The precipitation of a fraction in a given solvent implies the
inability of this solvent to dissolve all the asphaltene fractions having a lower solubility class index.
The solubility class of an asphaltene is little affected by its concentration in the oil. However, it can be strongly affected if
another asphaltene fraction is added or if it is fractionated by a partial precipitation. After a partial precipitation, the
precipitated fraction, once redissolved and noted, will get a lower index. That is why if asphaltene deposits is found in the
production equipments, these deposits will show an ASCI much lower than the ASCI found for the asphaltene fraction in the
oil. As it is implicitly said in the examples of asphaltenes having an ASCI note of 0 (0% heptane) or 20 (100% heptane), it is
possible to find asphaltenes being soluble in heptane, and asphaltenes being insoluble in toluene, in contradiction to the strict
"handbook" definition.

Application of the method

Predictive studies during field development phase : A fast screening method for the evaluation of the risk of
asphaltene precipitation due to pressure drawdown
As said in the introduction, measuring the ACSI only gives us the solubility characteristic of the asphaltene fraction. To
evaluate the stability limit of asphaltenes in given oils, this characteristic must be compared with the solubilization power of
the oil in the considered conditions.
The stability of an asphaltene fraction with a given solubility class in an oil or in a solvent mixture will depends mainly on
the molecular volume and on the density of the oil or of the solvent, and it is rather independent on the concentration of the
asphaltenes. For oils with similar molecular volume, the higher the density of the oil, the higher its capability to dissolve
asphaltenes. When the density is similar for two oils, the oil with smaller average molecular volume will have higher
4 SPE 161936

capability to dissolve asphaltenes. The asphaltene stability depends also slightly on the temperature. Generally, most of
authors found that at constant density of the oil, an increase of the temperature will increase slightly the asphaltene stability.
In Error! Reference source not found., the average molecular weight of reservoir fluids from our fluid database is plotted
against the density of the oil at reservoir conditions. For confidentiality purpose, values of the densities are not provided. We
can see that the two parameters are roughly correlated for the reservoir fluids found in our fluid data base, Thus, we can
consider the stability of the asphaltene fraction with a given solubility class as mainly density dependent. The ASCI of the
asphaltenes is measured for each of these fluids. In Fig. 3, the ASCI value is plotted against the density of the oil at reservoir
pressure. In this figure, the higher the density of the fluid and the ASCI, the more stable the asphaltene fraction in the oil. If
an asphaltene fraction is soluble in an oil sample, a higher ASCI asphaltene will be soluble in the same oil or in any oils with
the same or higher density. Therefore, the fluids potentially instable to be considered in the risk evaluation are all located in
the left-lower border of the graph (as indicated by the black bold line) : no fluid is found in this area, because the asphaltene
fraction would not have been soluble in the corresponding fluid. Consequently, this borderline is considered as the solubility
limit – an asphaltene fraction with given ASCI is soluble in a fluid with given density only if the couple is situated at the
upper-right side of the line.

This fast screening method allows us to focus our investigation on the high risk cases only. However, corrections need to be
done in case of high concentration of non hydrocarbon compounds.

Flow assurance assessment on field deposits : Are asphaltenes really responsible for the deposit ?
When a field deposit is found, asphaltenes are often thought to be the cause of the problem, and mitigation strategies are
looked at while the deposit is sent for more complete analysis. Usually, what triggers such a fast operational response is that,
when performing "classical" characterizations of the deposit, people find asphaltenes, and associate them to the problem.
Sometimes, the mitigation strategies taken to fight "asphaltene deposit" can turn out to be successful even if asphaltenes are
not at all responsible for it. But, it is also very common not to solve anything, or worse to increase the issues.
As a matter of fact, if there is oil in a deposit, asphaltenes of this oil will be detected in the deposit, whether they are or not
the cause of the deposit, and it is usual to take much more attention to the amount of asphaltenes rather than to their solubility
or the solvency of the oil. People will use parameters such as the spot test or the CII, Colloidal Instability Index, which is
defined as in equation 1 to get insight on the deposit.
!!!"#$%"#&'!!!!"#$%&'()("
Equation 1 !"" ! !
!!!"#$%#!!!!"#$%&'()

With these indications, extra heavy oils will generally be suspected to have issues related to asphaltenes, whereas, as a
contrary which can be illustrated through the De Boer's plot or in Fig. 3, they do have a lot of asphaltenes with a low
solubility class because they can dissolve them.
We received samples of deposit from an extra heavy oil field, for which the service company had diagnosed an asphaltene
related problem, and a sample of the oil produced on the same well. As the CII of the oil was 1.5 (considered as "critical"
risk), the deposit was thought to be an asphaltene deposit (Table 2). The ASCI of the oil was measured, and the deposit was
dissolved in toluene then noted in the ASCI procedure (Table 3). For both samples, the ASCI was 11 (55% heptane in heptol
to induce precipitation). This ASCI is well above the limit ASCI of asphaltenes that such an oil can solubilize. The deposit
was not at all coming from asphaltene deposition, but was linked to the size and the amount of solids produced in this well.
The mitigation strategies were thus changed, and more efficient solutions were implemented to fix the productivity issue.

Table 2 Data on EHO 1 Table 3 ASCI of EHO 1 and

deposit
Sample nC5 Insoluble °API Density (kg/m3) Saturated Aromatics Resins Asphaltenes CII Sample ASCI
EHO 1 13 8.5 1010.5 47.7 24.7 12.8 9.8 1.5
EHO 1 11
Deposit from well
producing EHO 1 11

Conclusions
A universal, phased approach to the prediction, verification, and treatment of asphaltene deposits has been described.
By defining a simple characterization procedure of the solubility class of asphaltenes at very high dilution, it is possible to
efficiently determine whether asphaltenes are or will be responsible for production offsets. If initial characterization indicates
a high likelihood of asphaltene deposition, a high-pressure test setup can facilitate confirmation, as well as evaluate
remediation options for the treatment of these deposits under flow conditions.

Acknowledgement
The authors would like to Total for allowing publishing this research. They would also like to thank their colleagues
Christian Hurtevent, and Benjamin Brocart for their contributions to these studies.
SPE 161936 5

References
[1] : S. Verdier, Experimental study and modelling of asphaltene precipitation caused by gas injection, PhD thesis, Technical University of
Denmark, 2006.
[2] : Boer, R.B.d., K. Leerlooyer, M.R.P. Eigner, A.R.D. van Bergen, SPE 24987 : "Screening of Crude Oils for Asphalt Precipitation:
Theory, Practice, and the Selection of Inhibitors", 1995
[3] : J. X. Wang, J. S. Buckley, SPE 64994, An Experimental Approach to Prediction of Asphaltene Flocculation, 2001
[4] : Jill S. Buckley, Jianxin Wang, Jefferson L. Creek, Solubility of the Least-Soluble Asphaltenes, 2007, pp 401-437 in "Asphaltenes,
Heavy Oils, and Petroleomics", Ed Mullins, O.C., Sheu, E.Y., Hammami, A., Marshall, A.G.
[5] : J. D. McLean, P. K. Kilpatrick, Effects of Asphaltene Solvency on Stability of Water-in-Crude-Oil Emulsions, Journal of Colloid and
Interface Science, V 189, I 2, 1997, pp 242-253
[6] : P. M. Spiecker, K. L Gawrys, P. K Kilpatrick, Aggregation and solubility behavior of asphaltenes and their subfractions, Journal of
Colloid and Interface Science, V 267, I 1, 2003, pp 178-193
[7] : M. Rondon, J. C. Pereira, P. Bouriat, A. Graciaa, J. Lachaise, J.-L. Salager, Breaking of Water-in-Crude-Oil Emulsions. 2. Influence of
Asphaltene Concentration and Diluent Nature on Demulsifier Action, Energy & Fuels, 2008, 22 (2), pp 702–707
6 SPE 161936

Fig. 1 : ASCI note for 3 solutions of the same asphaltene at 3 different concentrations going for 750 ppm to 30 ppm
12 (60% Heptane) 13 (65% Heptane) 14 (70% Heptane) 15 (75% Heptane)

2.5% Oil in Toluene

(~750 ppm asphaltenes)

0.5% Oil in Toluene

(~150 ppm asphaltenes)

0.1% Oil in Toluene

(~30 ppm asphaltenes)

250 20 100

230 18 90

210 16 80

Heptane in Heptane+Tolune, %
190 14 70
Molecular weight, g/mol

170 12 60
ASCI

150 10 50

130 8 40

110 6 30

90 4 20

70 2 10

50 0 0
Density @ reservoir conditions Density @ reservoir conditions

Fig. 2 : Oil Molecular Weight vs density at reservoir conditions Fig. 3 : ASCI vs density at reservoir conditions