REVIEWS

Asphaltenes in oil reservior recovery

LIAO Zewen & GENG Ansong
State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences,
Guangzhou 510640, China
Correspondence should be addressed to Liao Zewen (e-mail: liaozw@gig.ac.cn)
Abstract Asphaltene is one of the important compositions in oil reservoirs, while it is also a major
factor that causes difficulties in oil recovery and oil post-processings. Up to date, study on
asphaltenes in oil recovery is still a bottleneck problem. In this paper, the advances of studies on
asphaltenes are reviewed, and some directions for further studying are suggested. What is
reviewed in the paper includes the precipitation studies of asphaltenes, the degradation studies of
asphaltenes and the applications of asphaltene’s studying in oil recovery; furthermore, it is regarded
as a promising direction to study the possible applications of asphaltene’s selectively decomposing
by chemical reagents in oil recovery.
Keywords: asphaltenes, precipitation, oil recovery, chemical degradation.

Asphaltene is an important constituent in crude oils, while it is also a major factor that causes
difficulties in oil recovery[1,2]. During the evolution and migration of oil reservoirs, the asphaltenes may
be flocculated or precipitated out from crude oils due to the changes of pressure, temperature and/or the
compositions of reservoir fluid[3 5]. During the evolving of oil reservoirs, the precipitation of
asphaltenes is regarded as the main factor for tar-mats origin [6 9]. Tar-mats are the reservoir zones
containing petroleum highly enriched in asphaltenes (asphaltene 20% 60%) relative to the related oil
leg petroleum[6,7]. Tar-mats usually have a sharp boundary with the oil leg, and occur close to geological
discontinuities. The occurrence of tar-mats is generally detrimental to oil recovery, which changes the
wettability between oil and rock[10], presents low permeability or intra-reservoir flow barriers in oil
reservoirs. Deasphaltation problems are likely to occur during oil exploitation because of tar-mats[8,9],
which will cause great difficulties in oil production.
Owing to the alteration of ambient conditions, asphaltenes are liable to be precipitated out during
oil recovery, transportation and post-processing[1,2,11]. It can make oil production more arduous and
costly because of the partially plugging in oil well and pipeline by asphaltenes. It may further decrease
recovery efficiency or even stop oil production due to the shutoff of oil pore throat or even of the whole
oil well[2].
Regarding the pressing need in oil recovery, studies on asphaltenes are becoming a hot issue in oil
recovery and petroleum industry. The achievement of studies on asphaltenes up to date has made good
contributions to petroleum industry. However, with oil reservoirs being run out, it is emergent to study
how to upraise the recovery efficiency by secondary and tertiary productions, and further studies on
asphaltenes have special significance. The advances of studies on asphaltenes in oil recovery are
reviewed in this paper, and some directions for further study are suggested.
1 Studies on asphaltene’s precipitation
Asphaltenes, the most polar and heaviest compounds of oils, are insoluble in low normal alkanes
(nC5 nC8) and soluble in such solvents as benzene and toluene and so on. In crude oils, asphaltenes,
resins and petroleum alkanes compose a dynamic stable system[1,12], similar to a colloidal system, in
which the petroleum alkanes act as solvents, the asphaltenes as micelle and the resins as
stabilizers[1,12,13]. Owing to the changes of temperature, pressure and/or compositions in crude oils, the
dynamic stable system may be disturbed and even destroyed, and the asphaltenes are likely to be
precipitated out from crude oils[1,12,14].
( ) The theoretical models of asphaltene’s precipitation. Solubility-model first came into use,
including simple polymer solution theory and heterogeneous polymer solution theory[15,16]. The former
theory regards crude oil as a few fictitious pure compositions, and the asphaltenes precipitated out from
crude oil are regarded as a pure composition. Precipitation of asphaltenes is processed by the phase-

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equilibrium theory. This model is simple for application. However, to simplify the complex crude oils
as several pure compositions is far from the real state of oils. Therefore, the processed results are full of
doubts. The latter theory is improved by regarding the asphaltenes as an impure composition with a
continuous molecular weight range[2,14,17]. It applies heterogeneous polymer solution theory to handling
the precipitation of asphaltenes. However, this model requires thermodynamic processing, which is too
complex to be widely applied.
The above two models were derived from the Flory-Huggins solution theory, and have
preliminarily described the precipitation of asphaltenes. But both of them fail to pay attention to the
interactions of asphaltene/asphaltene, asphaltene/resin and asphaltene/(the other constituents in oils). It
has been manifested that these interactions are very important[1,2,12]. With respect to these interactions,
the early solubility theories have been further improved. Based on the heterogeneous polymer solution
theory, Mansoori[2] considered that asphaltenes, resins and petroleum alkanes are dependent on one
another, to form a dynamic stable system in crude oils[1,13]. The stability of this system is closely related
to the ratios of polar/nonpolar constituents and the ratios of heavy/light constituents in crude oils. From
this point, the phase-equilibrium equations of every heavy constituent were established to study the
precipitation of asphaltenes. This model has abandoned the hypothesis to simply regard the crude oil
constituents as perfect particles. It rationally pays attention to the interactions between constituents in
crude oils. From the view of this point, the gist of this model is similar to that of thermodynamic
colloid-model[18 24]. It has been considerably applied up to date.
Among the theoretical models on asphaltene’s precipitation, the thermodynamic colloid-model[13,25]
has been applied more widely and more successfully. It was put forward by the knowledge about the
dynamic stability of crude oils. This model was developed by Leontaritis and Mansoori[2,14]. It treats
asphaltenes as micelle suspending in crude oils. The stability of the system primarily relies on the
properties and concentrations of resins[1,21,26] as well as the equilibrium conditions between the surface
of asphaltenes and oil-base phase[15]. In this model, according to the theory of surface-chemistry, the
thermodynamic processing methods are applied to studying the precipitation of asphaltenes. This model
can reflect the real state of crude oils, then has been extensively accepted and applied.
Regarding the theoretical models of asphaltene’s precipitation, besides the above ones, there are
solid-model[15] and electro-chemical model[27 29] as well. The former takes the deposits of asphaltenes
as solid phase, and adopts the liquid-solid equilibrium theory to study the precipitation of asphaltenes.
The latter takes crude oils as a strong polar system. Owing to the strong polar functionalities and
hetero-atoms in asphaltenes[27,30], part of the asphaltenes exist as free ions or dipolar ion-pairs. It
presumes that the precipitation of asphaltenes is induced by the ionic parts.
In summary, there are comprehensively three viewpoints on asphaltene’s precipitation. The first
one regards the asphaltenes existing as approximate real solutions in crude oils[31], including solubility-
model and solid-model. The precipitation of asphaltenes is thermodynamically reversible. The second
one takes asphaltenes as micelle existing in crude oils. The precipitation of asphaltenes is kindled by
the disturbance of colloid balance state due to the changes of temperature, pressure andlor compositions
of oils. The process is thermodynamically irreversible. The third one considers part of asphaltenes as
ions occurring in oils. The precipitation is induced by the interactions among ions. From the view of
different aspects, all the three viewpoints are, to some extent, applicable respectively in different oil
reservoirs. Solubility-model is simpler than solid-model for application. Both of them directly regard
asphaltenes as the studying object. While the colloid-model takes resins as the studying object, and uses
the colloid-chemical theory to study the precipitation of asphaltenes. However, all of them can be
summarized as non-electrolyte solution models. On the other hand, the electro-chemical model is based
on electrolyte solution theory. The model can be applied well in low viscous oils, but invalid in more
viscous crude oils. It would better describe the precipitation of asphaltenes by combining the colloid-
model with the eletro-chemical model.
( ) The experimental studies of asphaltene’s precipitation. The experimental studies are mostly
focused on the making of the beginning point and the amount of asphaltene’s precipitation, while it is
relatively backward in the further studying on how to mitigate or even prevent the asphaltene’s
precipitation under oil reservoirs surroundings. The work can be primarily divided into two aspects: the

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studying on asphaltene’s precipitation models by normal experimental means and the simulative
studying on asphaltene’s precipitation under oil reservoirs surroundings.
With the recent advances in analytical technology and experimental apparatus, the methods for the
making of the initiative precipitation of asphaltenes have been greatly improved. The simplest one is by
visual observation [32]. The optical ones, which include light-scattering method[15], light-refraction
method[33] and fluorescence-analytical method[32] and so on, determine the initiative precipitation of
asphaltenes according to the sensitive changes of oil’s optical properties. In addition, there are other
means such as electric-conductivity method[27,28,32], viscosity-index method[34], surface-tension method[15]
and heat-conductivity method[35,36] as well. All these methods have some applicability respectively in
different oil systems, and should warrant sufficient sensitivity and maneuverability under oil reservoirs
surroundings.
There are two methods for determining asphaltenes deposit’s amount. One is to directly gather the
asphaltene’s deposits. The other is to measure some physicochemical parameters of oil systems to do it.
The determination of deposit’s amount is more questionable than the identification of initiative
precipitation. Data from different methods cannot be compared with each other.
Studies on how to mitigate or even avoid asphaltene’s precipitation are mainly carried out by
normal experimental means. Clarke and Pruden [36] consider that the phenanthrene-like compounds are
useful inhibitors for asphaltene’s precipitation. Chang and Fogler [26] believe that the resinous
compounds with multiplied functional groups are good stabilizers for asphaltenes. They pointed out that
these compounds might induce the co-precipitation between asphaltenes and resins. Simulation on how
to mitigate or even avoid asphaltene’s precipitation under oil reservoirs surroundings has not yet been
reported. There are great difficulties in this field due to the complexity under oil reservoirs
surroundings. However, with respect to the importance and urgency, it is undoubtedly a striving
direction along with the advancing in analytical technology and experimental apparatus.
2 Studies on asphaltene’s degradation
With regard to the studies on asphaltene’s degradation, there are a few references[37 39] reporting
the pyrolysis of asphaltenes. The results are manily applied in the other fields of geochemistry[40 43],
and have little to do with the oil reservoirs recovery. In this field, further studies on asphaltene’s
degradation are needed to meet the practical demands during oil productions.
Biodegradation technology[44 46] can reduce oil’s viscosity and upraise the recovery efficiency by
decomposing the heavy constituents in oils. This technology has been applied well and is likely to be
further improved during oil production [47,48]. The principles[46] of this method are to activate microbes
underground by injecting aerated water with the salts of nitrogen and phosphorus. The mechanisms[44]
include the following seven points: ( ) the carbon dioxides generated in-situ can increase pressure to
enhance the heavy constituents’ solubility in oils; ( ) the generated organic acids can improve the oil’s
properties; ( ) the large hydrocarbons can be degraded into small ones; ( ) the produced surfactants
can improved the oil’s solvency; ( ) the produced bio-polymers can scatter clotty oils; as droplets; ( )
the heavy constituents are improved by enzyme in oils and ( ) The oil’s viscosity is meliorated.
Nevertheless, there are limitations for this technology, since the microbes are liable to be destroyed
under oil reservoirs surroundings for high temperature, high salinity and abundant metal-ions. The
generated surfactants and bio-polymers themselves are likely to be precipitated out from crude oils[44].
Furthermore, the microbes are hard to cultivate. Regarding the further study on biodegradation
technology, the new microbes ought to be temperature-resistant, salt-resistant, metal-ions resistant and
easy to cultivate.
Chemical degradation of asphaltenes for biomarker studies[49] has been reported, while that
application in oil recovery has not yet been reported. It is meaningful to search the application of
chemical degradation in oil recovery, by selectively and to a certain extent decomposing the heavy
constituents dominated by asphaltenes in oil reservoirs. This study can not only increase the output of
oils, but also even bring forth fine economic profits in oil post-processings. Theoretically, it is not
difficult to find the right chemical reagents by normal experimental means. What is important is to
study the reagents’ validity under oil reservoirs surroundings and the economic feasibility. With respect
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to the potential and promising significance, it is necessary to probe into this field. With more
knowledge of asphaltene’s molecular structures and of studies on kerogen’s chemical degradation, the
preliminary studies can be started with tests on asphaltene’s oxidative degradation, reductive
degradation and free radical cracking, to find the right rreagents. Then try to apply these reagents under
simulative oil reservoirs surroundings, to search the applications of asphaltene’s chemical degradation
in oil recovery.
3 Studies on asphaltenes in oil production
Some achievements have beee obtained by reducing oil’s viscosity and increasing recovery
efficiency, to solve the problems caused by the heavy constituents dominated by asphaltenes in oil
recovery. Based on the water-drive, gas-drive[47,48] and thermal-recovery[50], the improved methods such
as alkaline-waterflooding[51], acid-waterflooding[47,48], surfactant-drive[52], polymer-drive[53] and micelle-
polymer drive[47,48] have been developed.
The early applied water-drive increases the oil’s recovery efficiency by driving the oil to
production well. The early-used water was directly from rivers or seas. Subsequently, according to the
different physicochemical properties and geological properties of different oil reservoirs, the improved
active water drive means, such as alkaline-waterflooding, acid-waterflooding and the other chemically
active water drives, have been developed. The main factors[46] influencing the drive efficiency include
the microscopic heterogeneity of porous medium in oil reservoirs, the wettability of pore surfaces, the
surface tension between the oil and the injected water, and the viscosity ratios of oil/water respectively.
Although the water-drive is still a main means in oil production, the further striving directions[51] should
be to improve the “quality” of injected water, and to look for more efficient oil-displacement agents
regarding to lessening the difficulties caused by the heavy constituents dominated by asphaltenes in oil
recovery.
The gas-drive is to inject carbon dioxides into oil reservoirs[46,48], to increase oil recovery
efficiency by improving oil’s viscosity, enhancing the solubility of heavy consitituents in oils, and
compensating for the pressure drop during oil’s recovering. The shortcomings of this means include
that the reservoirs’ sweep efficiency is not as high as that of water-drive. Due to not fully commingling
between oil and carbon dioxides, the light constituents might be extracted out from crude oils to make it
difficult to produce the residual oils. The development of this technology will be combined with water-
drive, by applying them simultaneously or alternately to producing more oils from the reservoirs.
The thermal recovery has been well applied to the production of heavy oils, asphalts and oil
shales[50]. It comprises the in-situ combustion and steam-drive means. This technology has special
superiority in upraising the heavy oil’s production efficiency, by reservoirs combusting to a certain
extent or by injecting hot water or steam to increase the reserviors’ temperature for enhancing the oil’s
fluidity and solubility. Although this technology has been extensively applied, however, there still exist
the problems such as great thermal loss and low energy efficiency and so on. Furthermore, the heat-
sensitive materials in oil reservoirs are liable to be destroyed. Especially for the in-situ combustion,
high quality oils may be transformed into useless cokes underground.
The technologies for upraising oil-recovery efficiency are briefly reviewed here. All the methods
have some applications respectively in different oil reservoirs with different physicochemical and
geological properties. Before applying these technologies, the reservoirs’ geological data and the oil’s
physicochemical properties must be taken into account as more as possible[54] to conclusively analyze
every method’s validity from the view of technology and economy. The further improving of these
technologies will rely on the right combinations of these methods, for example, the combination of
water-drive and gas-drive, the combination of thermal recovery and active water-drive, and so on.
When regarding the difficulties caused by asphaltene’s precipitation during oil’s post-processings,
based on the thermal recovery, it will be of great significance to research the applications of
asphaltene’s chemical degradation.
4 Conclusions
It is estimated[44] that there are above 60% of crude oils remaining underground after exploiting by
the present technologies within the world’s oilfields. The total amount of residual oils is by far more

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than the new reserves that can be found. With the oil reserviors on earth being run out, it will be an
emergent task to exploit the abundant residual oils by enhanced oil recovery technologies. Further
studies on asphaltenes are of special significance in oil recovery. With more knowledge about
asphaltene’s molecular structures and the detailed mechanism of asphaltene’s precipitation, the
appropriate strategies can be made to increase the oil recovery efficiency during oil productions. The
following two points will be the directions for further study on asphaltenes: ( ) the simulative models
in pursuit ought to warrant that the asphaltene’s precipitation can reflect the oil reservior’s surroundings.
The results should be of sufficient sensitivity and accuracy; ( ) studies on asphaltenes degradation are
combined with oil recovery, based on the kinetic studies of asphaltenes pyrolysis, to study how to
selectively decompose the heavy constituents dominated by asphaltenes in oil reservoirs, and to study
the applications of this technology to oil production.
Acknowledgements The authors are thankful to Prof. Fu Jiamo and Prof. Sheng Guoying for their helpful discussions and
suggestions. This work was supported by the Key Projects of Resource and Ecological Environment Research (Grant No. KZ952-
S1-435), the Chinese Academy of Sciences.
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(Received April 13, 1999)

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