SPE 101022
Development and Field Use of a Novel Solvent-Water Emulsion for the Removal of
Asphaltene Deposits in Fractured Carbonate Formations
S. Lightford, Halliburton; E. Pitoni, Eni S.p.A; F. Armesi, Halliburton; and L. Mauri, Eni E&P
Copyright 2006, Society of Petroleum Engineers
This paper was prepared for presentation at the 2006 SPE Annual Technical Conference and
Exhibition held in San Antonio, Texas, U.S.A., 24–27 September 2006.
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Abstract
The formation of asphaltene scale inside the tubing or in
the reservoir is a common problem associated with crude oils
in many parts of Italy and common to the industry as whole. In
Italy regular treatments using coiled tubing or washing by
bullheading are performed to re-establish production. While
asphaltene inhibitors can be injected into the tubing string,
asphaltenes can still create problems below the injection point
and plug the perforations, formation pores, and/or natural
fracture network systems.
There is a wide range of hydrocarbon-based solvents that
have been used in the industry to remove asphaltenes. The
more effective solvents have a low flash-point temperature,
making them expensive and hazardous. In addition these
hydrocarbon-based solvents leave the formation in an oil-wet
state after asphaltene removal instead of re-establishing the
water-wet condition that acts as barrier to slow down the
deposition of the asphaltene on the formation. This effect
accelerates the re-disposition of the asphaltene in the
formation and increases the speed of the production decline,
increasing the frequency of remedial treatments.
This paper describes the laboratory development and field
application of a water/aromatic solvent emulsion system that
has been successfully used to clean/dissolve asphaltene and
leave the carbonate fractured formation in a water-wet state to
delay the production decline. Other advantages when using
this type of emulsion are cost reduction and improved
effectiveness in removing asphaltene deposits, when compared
to alternative solvents that have been employed. This is of
particular significance to these wells where large volumes of a
washing phase have to be pumped downhole. Hazards have
also been reduced by using relatively high flash-point
aromatics. Continuous mixing of the emulsion when pumping
reduces waste and improves the logistics involved in pumping
the large volumes needed to treat long, openhole sections
and/or to treat the fractures deeper in the near-wellbore region.
Two successful field applications in south Italy will be
discussed in detail, describing the placement technique
employed and the results achieved with this new system.
These treatments will be compared to previous treatments
using a hydrocarbon-based solvent. In the first well, where
previous treatments had failed to make significant
improvements, following the application of this emulsion the
production was practically fully restored and the production
decline was significantly slower than previous treatments. The
second well treated was a long, horizontal wellbore; again the
emulsion and technique proved successful in returning the
production to previous levels and sustaining the new level for
an extended period of time.
Background
Asphaltene is well known in the industry for causing
production loss through plugging the tubing, perforations, and
formation. The term "asphaltene" is applied to the black,
carbonaceous components of petroleum; these compounds
occur in many crude oils in the form of colloidal, suspended,
solid particles. They are characterized by their insolubility in
light paraffin hydrocarbon solvents, such as pentane,
petroleum ether, etc. Chemically, the asphaltene fraction of
petroleum is composed of polycyclic, condensed, aromatic
rings with several side chains. These compounds have
relatively high molecular weights and are considered polar
materials because molecules of sulphur, nitrogen, oxygen, and
complex metals are present.
Asphaltene precipitation takes place when the crude oil
loses its capability to disperse and stabilize the particles. The
asphaltene stability depends on the composition of the crude
oil, temperature, pressure and the nature of the reservoir rock
surface. Under static reservoir conditions, asphaltenes are
normally held in a stable suspension by resins, a family of
polar molecules. Changes in fluid temperature and pressure
that are associated with oil production from the reservoir may
cause the asphaltene to flocculate and precipitate out of
suspension and adsorb to the rock or pipe surfaces.
Additionally, the asphaltenes may flocculate because of
electrical charges created by the motion of flowing
hydrocarbons. Asphaltenes may also flocculate by mixing of
different oil types, for example, along a flowline collecting oil
from different wells/reservoirs. To further compound the
problem, emulsions can be stabilized by asphaltenes.
2 SPE 101022
Regardless of the mechanism causing the asphaltene to deposit
the result is a plugging effect that inhibits or reduces oil
production. Precipitation of asphaltene particles may also
provide nuclei for paraffins to start precipitating e.g., in the
case of the wells discussed in this paper where the deposits are
frequently a combination of asphaltene and paraffin, often
associated with inorganic material such as formation solids,
salts, and iron oxides.
While a lot of work has been conducted in the industry to
address the problem of asphaltene deposition, there are no
established industry practices or guidelines to:
• Identify the problem in the early stages of the production
decline.
• Determine if and at what point in the reservoir’s life the
asphaltene will become a problem.
• Determine the best materials/solvents to remove the
asphaltene.
• Determine the best method to evaluate effective inhibitors
to delay or prevent their formation.
The lack of industry standard practices is justified by the
variable nature of the asphaltene problems that depend on the
reservoirs conditions and the chemistry of the oil. Intervention
treatment design and timing is generally based on local
practices that are put in place to manage the problem. In the
field described in this paper, there had been long established
practices to determine the timing and the method of the
intervention. However, the same practices were no longer
achieving the success of the past: the severity of the problem
is increasing with the age of the field. To improve on the
performance of the treatments with the changing reservoir
conditions, a review of the local practices was implemented. It
was during this review that the emulsion system described in
this paper was developed. The remainder of the paper
describes the methods used to develop and optimize the
solvent, leading to the development of the emulsion system.
This emulsion system was then applied in the field. Two case
histories in two different well configurations (perforated
casing, and horizontal open hole) in the same field are
described to illustrate the application.
Process of Asphaltene Deposition, Removal and
Prevention
Asphaltene/Paraffin Deposition
Fundamental to solving any problem is having a good
understanding of the processes involved. In recent years,
considerable work1-7 has been done to further understanding of
the mechanism and chemistry of the asphaltene flocculation,
deposition, and adherence to surfaces. The modern
understanding of the deposition process can be summarized as
follows:
• Asphaltene deposition process is controlled by the
thermodynamics of the system,8 i.e. temperature,
pressure, composition of the oil, and surface conditions of
the rock. Only when these conditions change can
flocculation and deposition of the asphaltene occur.
• Crude oils contain asphaltene and polar elements (resins)
that are deposited onto to the rock surface following a
Langmuir 1 or Type 2 curve, which are characterized by a
steep slope at very low concentrations.9 While the
Langmuir curve would indicate that a point of stability is
reached quickly, research has shown that this can
continue at a much slower rate and does not stabilize.7 In
addition to the asphaltene, lower molecular-weight
components, such as resins, also adsorb on the rock or
tubulars but not as strongly as the larger asphaltenes.4
• More polar asphaltenes, which contain a larger percentage
of hetero-elements, adsorb even more strongly and alter
the rock surface more toward being oil-wet.2 For example,
polar constituents can penetrate the water film and
compete with water for active sites on the rock surface,10
replacing the connate water.
• The presence of water also affects the adsorption process.
Experiments on water-wet rock show a considerable
reduction in adsorbed asphaltenes.1,2,11,12 The stability of
the water film on the formation is one of the factors that
determines this reduction and is a function of ionic
strength and pH.11
• It has been shown that asphaltenes can precipitate in the
formation resulting in pore plugging.7 Other experiments
have shown that asphaltene will not travel far once they
are de-stabilized and are deposited quickly once this
destabilization begins, hence the damage zone is likely to
be quite small.13 However, if the deposition is likely to be
high, severe core plugging occurs in a relatively short
time frame.
• Paraffin separates from crude oils when the temperature
of the oil cools sufficiently. Fines, such as sand, silt, and
asphaltenes often speed this separation process. These
small particulate materials suspended in the crude act as
nuclei for the crystallization of the small wax particles
suspended in the oil into larger particles. Thus, paraffin
problems greatly increase when these fines are present
and can be created in presence of asphaltene deposition in
conditions where this might not normally occur.
Under normal production conditions deposition cannot be
stopped: it might only be delayed by controlling the
production rates to minimize the changes in thermodynamic
conditions that cause the precipitation.
Delaying the Deposition Process
Because the composition of the produced fluids is fixed, the
only factors that can be controlled to delay the deposition is by
producing the well with the aim of eliminating the
thermodynamic conditions to cause the flocculation and or to
modify the surface of the rock or pipe by coating the surface.
Controlling the Thermodynamic Conditions
To produce oil from a reservoir, the thermodynamic
conditions of the fluid must change, resulting in a drop in
temperature and pressure, causing the deposition of the
heavier organic compounds.8,14 Pressure has little or no direct
effect on increasing the solubility of the heavier organics in
crude oil, however it holds dissolved gases and volatile
constituents in solution. Pressure assists in maintaining the
asphaltenes in solution at the temperature of the formation.
SPE 101022
The deposition of the heavier organic solids can occur
where the thermodynamic state is changed. In producing the
reservoir, significant change occurs when there is a pressure
drop needed for production, i.e. at the pore throat, inside the
natural fractures, and as the fluid enters the wellbore and
moves up the tubing to the wellhead. For instance, asphaltene
solubility is reduced by reducing the fluid pressure down to
the bubble point. The greater expansion of the paraffin portion
while reducing pressure, compared to the minor expansion of
the aromatic fraction, practically increases the paraffin
volumetric fraction of the crude and destabilizes the
asphaltenes. It is like adding a paraffin oil or solvent to the
crude, causing asphaltene flocculation and precipitation.
Below the bubble point, light paraffin components are released
by the oil as a gas phase and the aromatic fraction can grow
again in the liquid phase, stabilizing the asphaltenes again
because of the minor paraffin volumetric content. Hence,
asphaltene deposits can occur in each area, leading to plugging
and loss of production.
Under ideal conditions the well should be produced at
production rate such that the flocculation and deposition will
not occur.8,15 In managing the reservoir, the issue becomes one
of balancing the production conditions and production rate
with one that will reduce the production loss through the
deposition of the asphaltene and or delay the timing of the
intervention. In the field discussed in this paper, these actions
are being taken, but inevitably the problem still requires
regular intervention treatments. Monitoring the production
pressure and flow and the trend of the decline is important;
however, generally once this effect is seen in the surface data
a rapid production decline will occur that can result in the loss
of the entire production from the well until an intervention is
performed. Correct well management involves making a
decision at the right time to treat the well comparing the loss
in production to the cost of the treatment. Experience in this
field shows that an important further consideration in this
decision is that the longer the problem exists the more difficult
it is to treat, especially in long, naturally fractured intervals.
Modifying the Rock or Pipe Surfaces
Although the surface of the pipe or formation cannot be
changed, the material coating the surface can be changed.
Surface conditions that favor the accumulation of deposits are
oily coatings, surface roughness, and electrically chargeable
materials. All these exist in the formation matrix and tubulars.
Water-wet surfaces have less tendency for the deposition of
asphaltenes; asphaltene inhibitors can also be used to coat
surfaces.
Some inhibitors are designed to function so that they
disperse and adhere to the surface in preference to the
asphaltene from reservoir fluid thus delaying or preventing the
deposition.7 For the inhibitor or water-wetting agent to be
effective in delaying the re-disposition they must first adhere
to the surface and this requires a clean, asphaltene-free
surface. In the case of the tubulars this is relatively easy to
achieve by washing with suitable solvent combined with
jetting for mechanical action; subsequently, an inhibitor can be
injected through an injection nipple if the completion design
permits.
3
In the field described in this paper, injection nipples are
placed as close to the production packer as possible and
inhibitors are injected to delay the problem occurring inside
the tubing, if the well design permits. However, the lower part
of the well and the formation remain unprotected. In an
attempt to protect this area of the wellbore during well
interventions the use of squeezable inhibitors has also been a
common practice. These have been placed in the solvent or as
an overflush in an attempt to delay the deposition on the
formation in lower wellbore by their slow de-adsorption and
back-production with the oil. This creates a more stable
condition for asphaltenes, which in turn remain stable in the
bulk oil for a period of time long enough to produce them at
the surface, avoiding deposition.
Coating the formation surface with water or an inhibitor is
far more difficult. Laboratory work indicates that complete
removal of the asphaltene is not achievable and therefore the
rock surface can only be partially cleaned. Cleaning should,
however, be as complete as possible and the key to a
successful treatment relies on the asphaltene-removal process
so that the asphaltene coating can be replaced by water and/or
an inhibitor.
Removal
As described earlier, it is necessary to remove the asphaltene
from the tubulars and/or the formation face and pores, but
ideally it is necessary to leave all surfaces in a condition that
will prevent or slow down asphaltene deposition once the well
is back on production. Based on earlier published work and
internal core-test studies, the following factors are all
considered to be keys to a successful, long-lasting removal
treatment:
• Deposits have different solubility in different solvents,
dependent on the type of asphaltene in the crude.16 Co-
solvents can be added to the solvent to improve the
efficiency of dissolution of the asphaltene and generally
they will also improve the de-adsorption from the
formation surface; therefore co-solvents serve two
beneficial purposes in the removal process.
• Though it might be possible to remove/de-adsorb the
asphaltene, in the wrong environment these will be
immediately re-adsorbed onto the formation or rock,
either during the removal process or when placing the
well on production. To prevent the re-adsorption these
polar sites need to be occupied by other polar chemicals
that have a greater affinity for the rock surface; asphaltene
inhibitors and/or water can be used for this purpose.
• Because asphaltenes have a higher affinity to adsorb onto
surfaces with a similar structure, that is, on core surfaces
with adsorbed asphaltenes,5 cleanup of asphaltene-
damaged wells should be as thorough as possible. It is
well known that simple solvent treatments, with toluene
for example, are usually not very effective because their
effect lasts for a few days/weeks only. Treatments with a
water-based fluid are much more promising and are
reported to remain effective over several months.17
• To dissolve and remove the asphaltene from the rock/pipe
surface requires a strong polar solvent that not only takes
the asphaltene in solution but also breaks the molecular
4 SPE 101022
bond of the asphaltene, which retains it to the surface of
the formation. Experiments have shown that cleanup with
pure toluene removes most of the asphaltene fraction but
the surface will still be covered with asphaltenes.18,19 The
nature of the remaining asphaltenes is likely to be the
most polar and highest molecular weight fraction. As a
consequence, the core surface will still be intermediate to
oil-wet. Because an asphaltene-covered surface is more
prone to redeposit of asphaltenes,11 cleanup should be as
efficient as possible.
• Besides film formation, the presence of water can be
beneficial since it can compete with asphaltenes for active
sites on the rock surface. However, from the literature as
well as in-house experiments, desorption of asphaltenes
cannot be achieved fully. In other words, the rock surface
can be changed to intermediate-wet at best.
• It has been demonstrated that the wettability of a core can
be changed from water-wet to oil-wet by a Dean-Stark
extraction because toluene strips the water off the
formation core surface.1
• Effective plugging can occur because of mechanical
plugging and damage can be removed by injection (flow
reversal) of an inert fluid; this benefit, however, will be
short-lived, because the asphaltene will be deposited on
returning the flow (in a similar manner to a well as
damaged by mobilized formation fines).
Treating the surface of the rock and tubulars requires a
well intervention and injection of solvents to remove the
adhered asphaltene both from the pore space and as much as
possible from the rock surface to slow down the deposition
process. Complete removal from the rock surface has proven
to be difficult or impossible in laboratory conditions so given
the more complex nature of a wellbore and the inefficiencies
involved in fluid diversion in long perforated or openhole
sections, complete removal is unlikely to be achieved during a
well-intervention treatment. To maximize the effectiveness of
the treatment is not a question of selecting the most effective
and strongest solvent, but in addition the surface coated with
the deposits should be left such that the next deposition
process is delayed. This can be achieved if the maximum
possible amount of the asphaltene coating is removed from the
surface and is left water-wet, and/or is coated with suitable
asphaltene inhibitors during the treatment.
Development of the Emulsion
General
It was noticed that interventions performed in the field in
South Italy were becoming less effective and shorter-lasting
than in the past. To try and improve the design of the
intervention it was decided that a detailed review of the
current solvent being employed should be made for several
specific reasons:
• Improve the solvency capacity of the solvent being
routinely employed thus improving the cleanup
efficiency.
• The dissolved asphaltene, while still in the solvent used
for the treatment, was being immediately re-adsorbed
onto the metal surface of the tubulars, as was illustrated
by the condition of the coiled tubing (CT) equipment
pulled out of the well after several interventions. Fig. 1
shows the condition of the coiled tubing tools as a
consequence of the accumulation of asphaltenes inside the
riser during a well-washing operation.
• There was evidence from the production declines and the
failure of the solvent treatments to re-establish previous
production levels in some wells that the deposition of
asphaltene was occurring deep in the natural fracture
system inside the formation. The depth and extent of this
damage was difficult to determine, however, it was
envisaged that much larger amounts of solvent per meter
of interval were needed to penetrate deeper into the
natural fracture system.
A constraint on the review was that to perform this work
quickly the testing needed to be performed predominantly in a
field laboratory with limited resources, hence the test method
and measurement of the performance of the products needed
to be simple.
Issues Related to Sample Source
The first issue to be addressed in the laboratory was the
selection of the samples to be used to evaluate the solvents and
co-solvents. Asphaltene samples used in the laboratory are
generally prepared by mixing a crude oil with an aliphatic
hydrocarbon like n-hexane. The composition of the
precipitated asphaltenes can be varied by using a lighter
alkane or heavier alkanes. For example, in propane
asphaltenes precipitate, but also resins and other heavy
hydrocarbons, while in decane the “harder” asphaltenes
precipitate but few resins.4 Regardless of the above the
composition of the deposits in the well will most likely be
different from those produced in the laboratory,19 with
downhole asphaltene samples normally containing a much
higher fraction of the more polar, insoluble asphaltenes.
Solvents that are regularly applied in the field, such as toluene
and xylene, will usually dissolve only 50% of a typical
downhole sample. In addition, the deposits in the wellbore are
typically not only asphaltene and can comprise other organic
or inorganic deposits in addition to water.
Based on the above, downhole samples are preferred but
there are difficulties in obtaining sufficient samples of the
material for comparative testing purposes. In addition,
downhole samples from one well are likely to be different
from samples collected in another area of the field. Further, a
sample of asphaltene plugging the side of the tubing may not
be the same as the material plugging the permeability in the
formation. A compromise needed to be made and therefore it
was elected to follow these procedures:
• Downhole samples would be used for all the tests when
available.
• Samples taken from surface separaters and surface lines
would be used if downhole samples were not available.
• If samples from the well to be treated were available,
these would be checked with the standard composition of
emulsion to help ensure that it gave acceptable results.
SPE 101022
An analysis of the asphaltene sample would also be
performed when needed to determine the amount of
asphaltene, paraffin and other organic and inorganic material
in the sample. A typical analysis of sample from South Italy is
presented in Table 1. What was considered important in this
work was that regardless of the sample source, the selected
treated fluid would be equally effective in the dissolving
capacity in the laboratory and therefore there was confidence
that it would be successful in the well conditions.
Solvent Selection
General
A number of theoretical methods exist to determine the
optimum solvent for a particular asphaltene (Kauri-butanol
number, Hildebrand solubility parameter16 and Hansen
solubility parameter). The variable composition of asphaltene
samples should be considered. The simpler approach in this
situation was to try different solvents and determine the
amount of residue after applying the solvent for a period of
time at a specific temperature, mimicking the conditions
during a treatment. Because there was a high level of residue
using high flash-point solvents required by the field for safety
reasons, only the addition of co-solvents (high-polar solvent)
was made to determine if the residue could be further reduced.
The approach taken can be summarized as follows:
• Test the solvent currently being used with the field
sample and then test with toluene and compare the results;
this was used because it has the highest Kauri- butanol
rating of the common solvents so provided a base line to
compare results.
• Add a co-solvent to the solvent in use in the field to
determine if this could improve the result and then
optimize the concentration of the co-solvent.
• Repeat the tests using higher-flash point solvents to arrive
at a suitable solvent/co-solvent system that has a
sufficiently high flash point that is could be used safely in
the field with improved results in terms of asphaltene
solvency.
The test procedure, detailed in the appendix, is based on a
standard company procedure. This procedure was modified to
represent the conditions expected with the regard to the
contact time of the solvent at the bottomhole temperature,
instead of the standard 4-hour test we used a 1-hour test
period.
Results of Solvent-Only Testing
Testing quickly established that with the downhole
samples, a large amount of residue was remaining after using
the current solvent, a wash oil comprising distillates (coal tar),
naphthalene oils, and methylnapthalene fraction (OLG). A
proprietary co-solvent was then used in conjunction with
solvents and it was found that the co-solvent improved the
performance of the base solvent; the residue went from 24%
down to about 2%. Toluene resulted in less residue, (6%)
without the use of a co-solvent; this was expected, however
when adding the co-solvent the residue was further reduced to
a negligible amount. Downhole and surface samples were
5
tested with similar results (Fig. 2). Based on the successful
initial laboratory tests with the co-solvent it was decided not to
evaluate further co-solvents. Although the solubility was
comparable between the xylene added with co-solvent and
OLG, the appearance of the samples was vastly different. The
xylene and co-solvent had only a small amount of adherence
to the glassware used in the testing whilst the OLG had a
strong affinity and left sticky deposits that were difficult to
clean. This was not purely a problem seen in the laboratory;
field work had also indicated that this was reducing the
effectiveness of the treatment. There was clear evidence from
the condition of the downhole CT tools used on the cleaning
operation that deposition of solids was occurring; this in fact
had created some operational difficulties during well
interventions (Fig. 1). The most likely cause of this stickiness
was that the higher polar fractions of the asphaltene, while
being absorbed in the solvent, were immediately attaching to
surface sites as soon as available or when the solution
eventually became saturated. If this was happening to the
toolstrings being employed it could be surmised that this was
also occurring in the tubulars and the formation. Moreover,
OLG was considered unsuitable for well treatments because
the foreseen use of acid in some of the treatments; OLG is
acid-sensitive because it contains components which are
precipitated by hydrochloric acid, making both the residual
solvent ineffective and the acid partially spent by the reaction.
In the laboratory testing any residue that was left on glass
was also not being measured on the filter paper, which was
distorting the results. In summary, having a fluid that
prevented this immediate deposition of the asphaltene was
thought to be the key to improve the performance in the well.
Handling and Safety at the Wellsite
If the existing solvent was to be replaced, the safety issues
in handling and pumping the fluid had to be addressed. The
main issue of concern was the flash point. For the fluid to be
pumped safely without resorting to complicated handling
procedures the flash point needs to be maintained at well
above the maximum ambient temperature conditions,
generally a minimum of 5° C is used. The OLG solvent
currently employed had a flash point of 90° C so could be
stored safely in standard tanks, with suitable valve material.
Because of the large volume treatments being planned, toluene
(flash point 6° C), while being the best-performing solvent in
the laboratory, was seen to be too hazardous for the use in the
field. A similar situation also applied to the use of Xylene
(flash point 28° C), which could be used during the cold
winter and cool spring months, by using inert blankets on the
tanks of fluid to enable safe storage and pumping; this
procedure would not be acceptable in the summer when the
ambient temperatures are in 30° C range.
A further complicating factor in Italy is that any
commercially available industrial solvents that could be used
as fuel must contain a contaminant to prevent them from being
used as a fuel. If a contaminant is not added a tax penalty is
paid regardless of the use. Some of the contaminants used
were found to have a negative effect on solvency power of the
base solvent, increased the flash point, or were potentially
damaging to the refinery catalyst (e.g., chlorine-based
compounds).
6 SPE 101022
Based on in-house testing work previously completed, a
list of potential suitable solvents was compiled (Table 2). A
search of the local market was made and any solvent that
could be supplied in sufficient quantities (150 m3) with a flash
point above 55° C was considered suitable and tested using
field samples from South Italy. Eventually, a higher flash
point (66° C), heavy aromatic naptha solvent was found that
yielded similar results to the Xylene (listed as the Solvent 3 in
Table 2). The local available solvent was, however,
contaminated with 10% of 1-Methoxy-2-Propanol Acetate;
this contaminant was found compatible with the refinery
catalyst and has a higher flash point than the base solvent and
did not appear to affect the solubility results in the laboratory
testing.
Justification and Development of the Emulsion
A water-based fluid system was being tested to remove
asphaltene and organic debris from the tubing before tubing
removal during workover operations; this process minimizes
problems that would accompany handling contaminated
tubing. Various well washing surfactants (detergents) were
being tested.
It is well understood that the addition of surfactants21 can
be used to disperse organic deposits in the water phase and
assist in removing these deposits from surfaces. These
removed organic deposits are not generally taken into solution
and are dispersed in the water phase, ideally as fine particles.
After trying a number of different surfactants, we found a
surfactant that was particularly effective in breaking down the
samples of the deposits from the tubulars in the wells in South
Italy. Fig. 3 shows the dispersed sample in the water phase
following heating. When washing tubing, the dispersion
processes is assisted by a large amount of mechanical action.
Mechanical action is generated from turbulent flow created by
the high flow velocities from the rig pumps; turbulent flow not
only erodes the particles from the surface but also carries the
dispersed solids to the surface for disposal. In the case of
treating a formation, there is not the mechanical action
available for erosion to be effective and injection of the
dispersed solids could create further plugging in the
perforations, formation natural fractures, and pores. Initially
consideration was given to injecting this type of flush in
alternating stages with the solvent. An alternative was to
combine the solvent with the water flush in an emulsion.
If a solvent could be introduced into the water-based fluid
a very effective solvent would be capable of dispersing the
deposits and allow them to be quickly absorbed by the solvent.
The solvent and the water-based wash fluid were combined at
a 50/50 concentration. This produced an unstable emulsion.
Repeating the standard solubility test using the emulsion gave
a result that surpassed the solvent-only system. The emulsion
was found not only as effective in dissolving the asphaltene as
the base solvent but appeared to do this more quickly and
leave a much cleaner residue (Fig. 4).
The appearance of the all laboratory equipment following
dissolution of the deposits showed that it was water-wetting
and there was little to no adhesion of the dissolved asphaltene
on the equipment. Further tests using core material also
indicated this strong water-wetting capability of the emulsion.
Using a large amount of water in the solvent also meets the
second criteria of permitting greater volumes to the used
without storing great volumes of solvent. Combining the well
wash fluid with the solvent had resulted in retaining the good
dissolving capacity of the solvent-only system, which (1)
addressed the issue that greater treatment volumes could be
used and (2) held the possibility that the water-wetting
capability of the emulsion might delay the re-deposition of the
asphaltene.
Optimization of the Emulsion
Once it had been established that a solvent/water emulsion
could be used to remove the deposits, optimization was
necessary to determine the maximum amount of the water
phase that could be used in the emulsion. Maximizing the
water phase reduced the cost of the solvent per unit volume
and also would permit larger volumes of material to be used
for deeper penetration in the formation.
Solubility parameters of the solvent phase are determined
by the type and amount of the organic solvent, co-solvent,
surfactant(s), and water content. This determines the amount
of asphaltenes and other organic components in the deposits
that can be taken into solution. Dependent on the organic
components in the deposit, the solvent capacity will vary and
therefore to determine the capacity of the solvent requires a
fixed/known sample of the deposit. In this work we took a
more holistic approach to the problem and decided on a fixed
quantity of deposit to test and determine if this could be taken
into solution. This approach, however, leads to a further
question of how much solvent capacity is required to treat a
formation.
To determine if the emulsion system would dissolve
significant amounts of solvent a test was done with increased
amount of deposits and instead of using the standard 5 grams
per 100 mL as in the standard test, six times this amount was
added (30 grams). Translating this to the well, this would
relate to the removal of 300 kgs (about 300 L based on an
assumed density of asphaltene of 1.0 sg). The increase in
volume of the sample from 100 to 130 mL after the absorption
of the deposits confirms this solvency power and deposit
removal capacity. While this is possible in the laboratory, the
situation in the well is somewhat different, since some of
solvent will be absorbed by the formation fluid before coming
into contact with the asphaltene and therefore will be less
effective. To remove all the deposits from a completely
plugged tubing would require 3 to 4 times the tubing capacity.
However the aim of this work was to better treat the formation
and a comparison to the dissolving power of stimulation fluids
such as acids was thought to be more applicable. The
dissolving power of a 15% acid is of 220 kg/m3 of calcium
carbonate, which based on a rock density 2.72 sg,. is capable
of dissolving or opening up a pore volume of 80 L/m3. Using
this comparison indicates a significant dissolving capacity of
the solvent which has over three times the pore opening or
damage removal capacity of the 15% hydrochloric acid. Deep
formation penetration of the active solvent would be
anticipated with this level of dissolving power of the
emulsion. The cleanup process of the asphaltene is envisaged
as similar process of damage removal in sandstone formation
where the rock matrix is not dissolved but the plugging
SPE 101022
material is removed from the pore spaces to a depth beyond
the damaged zone.
Following further testing using 30 g of sample per 100 mL,
a formulation using a 66% water-surfactant phase in
combination 34% organic (xylene) solvent and co-solvent
phase was found to be more suitable and effective. The
resultant formulation was capable of dissolving 0.3 g
deposit/mL of solvent, considering that the currently used
solvent-only system (OLG) that was leaving 24% residue
(tested at 0.05 g/L only) using the same samples (Fig. 5). The
emulsion combined with the deposit was not excessively
viscous and could pass through the filter paper leaving only a
slight coloration of the filter material. The saturation point of
the deposit in the solvent was never fully defined; however the
testing indicated that 30 g/100 mL (or 300 g/L) was close to
the limit.
Diversion and Placement Issues
At the start of the project, an in-house information/data
search was completed on laboratory studies that had been
performed to solve similar problems. Extensive core-flood
testing in a sandstone core had previously been completed in
the evaluation of different solvent treatments; this included
some emulsions with 10% water. The cores used for this
testing had been damaged in the laboratory with asphaltene
extracted from the crude oil that was injected and then baked
on the core in an oven. Subsequently solvents were injected
into the core to remove the damage. During injection the
effluent was monitored for asphaltene, the regained
permeability tested, and the core split and examined by
scanning electron microscope (SEM). It was noticed that when
injecting the various solvents into the cores to remove the
asphaltene damage, successful removal of asphaltene was
accomplished only when there was an initial increase in the
injection pressure. The researchers involved explained this
phenomenon as a process that when the asphaltene adsorbs the
solvent into the organic coating this causes the coating to
swell and reduces the effective pore diameter. Therefore it
would be expected that in a well treatment an increase in
pressure could be expected when the solvent enters the
formation and begins to remove the asphaltene/deposits.
In the case of using an emulsion a second factor that could
give rise to an increase in wellhead pressure during injection
of the solvent is an increase in viscosity of the water phase. As
the asphaltene is taken into solution the O/W (oil-in-water)
emulsion incorporates more oil and asphaltenes in the internal
phase and the internal oil phase ratio increases with a
corresponding increase in viscosity. Emulsions can have a
severe damaging effect on the formation and this has been
demonstrated both in wells and in the laboratory; therefore, in
general; emulsions should be avoided.22,23
There is also evidence to indicate that more stable
emulsions cause a greater extent of formation damage.
Formulations that are considered unstable, i.e. with a break
time in the order of a few minutes at ambient temperature, do
not cause significant damage and are acceptable. Also if the
emulsion viscosity enables it to be removed from the
formation under normal production conditions it can be
considered undamaging. In the fields considered for treatment,
production is from an extensive natural fractures system not
7
from the pore spaces in the formation; therefore unless the
created emulsion was extremely viscous it was felt that the
formation would produce this emulsion in the returned fluid
without creating a problem of damage to the formation. In
case of using solvents with high levels of asphaltene
absorption it was noticed that the solution can become viscous
on initial contact with the solvent, but with time, absorbs the
asphaltene and returns to a thin fluid.
Increase in injection pressure from increasing viscosity
may be used as a method to divert fluid across the interval
being treated; examples of this usage are gelled acid systems.
If the increasing viscosity is seen in the well by the
corresponding increase in wellhead pressure then this may
have a positive effect in diverting the fluid into untreated areas
of the formation. Providing that the treating fluid returns from
the formation carrying the dissolved deposits this effect was
seen as a possible benefit during the treatment.
Laboratory to the Well Site
At this point it was decided that sufficient laboratory work
had been completed to justify a trial treatment in a candidate
well. The laboratory testing had proven that the fluid had met
the first two criteria as detailed below:
• Improve the dissolution of the field samples.
• Maximize the amount of solvent that could be used at the
well site.
The emulsion system was also water-wetting the
laboratory equipment and a wettability test using formation
samples taken from stones returned to the wellhead confirmed
that the emulsion would water-wet the formation. It was
thought that this water-wetting capability would also assist in
meeting the third criterion (longevity of treatment); longevity
could only be evaluated with a field trial.
Since the emulsion created is unstable and separates into
two phases in a matter of minutes, the emulsion cannot be
stored at the surface unless it is placed in tanks that are
agitated. Agitating tanks was not considered practical for the
volumes needed to treat these long production intervals, and
because of safety issues related to agitating tanks containing
flammable liquids. To overcome this problem it was decided
that the best approach was to continually mix the emulsion as
it was pumped downhole. The safest place to do the mixing
was in the high-pressure in the area immediately before the
lines entered the wellhead. A surface system arrangement as
shown in Fig. 6 was used to complete injection and pumping.
Equipment was arranged so low- or high-rate injection could
be performed. Low rates were needed during injection into the
CT equipment; high rates would be used when bullheading the
fluid. Using this method of mixing permits larger treating
volumes to be used (450 m3 instead of 150 m3) with the only
additional equipment of tanks for the storage for the water, in-
line high-pressure mixer, and suitable liquid-additive injection
pumps.
Using this mixing system there is also less waste because
tank bottoms are minimized and if the operation is terminated
early, the base materials could be reused.
8 SPE 101022
Case Studies
Background
In southern Italy several wells are producing from a
naturally fractured, carbonate reservoir at a vertical depth of
3200-3800 m. Oil is 30- to 40-API gravity with an asphaltene
content of 0.5 to 0.7%. The wells in the field flow without
artificial lifting, have very low water-cut, and are prolific
producers. The reservoir was discovered in the 1980’s and is
the largest active onshore field in western Europe; there are
approximately 40 producing wells in the field. Well profiles in
the field vary from the older vertical well designs with dual
completions in place to extended-reach, Level 5 multilateral
wells. The reservoir is in a national park, so drilling sites are
severely restricted and the current practice is to drill multiple
extended-reach wells or wellbores from a template site.
Multilaterals are becoming common and wellbore extensions
in excess of 3000 m, with over 2000 m of open hole producing
from different naturally fractured areas are common.
In the early life of the field there were no problems caused
by asphaltene deposition.8 However, as the reservoir pressure
has declined, production losses from asphaltene deposition
started to occur and are becoming increasingly severe. To
reduce the accelerated production decline by asphaltene
plugging, the newer wells have been completed with tubing
that has been fitted with downhole injection lines and
asphaltene inhibitors are injected at packer depth. However,
while this might reduce scaling in tubing and surface lines, it
does not protect the long openhole sections, fractures, and/or
slotted liners and perforations from becoming plugged.
Reducing production loss from damage caused by the
asphaltenes is an essential part of managing production from
the field.
Acidizing has been used in the past to treat the formation
and bypass the damage caused by the asphaltene in the near-
wellbore area, though operators prefer to avoid this solution
unless the problem cannot be solved with a non-formation
reactive solvent. The reasoning behind this approach is that
excessive acidization of the wells might lead to creating an
unstable wellbore and or increased water production. In the
past, acid had also not been successful in preventing the re-
disposition of the asphaltene or in stimulating the well at all.
The aim was to find a solvent system that would best re-
establish production without creating new flow paths in the
formation.
Case Study 1 - Vertical Well Southern Italy
Description and Treatment
The selected well for the pilot test was not typical for the
field and was completed as a dual-tubing completion.
However, this well was chosen because of the severe nature of
the asphaltene plugging, which had completely plugged the
long string and reduced the flow to a minimum in the short
string. In addition, two previous interventions with solvent and
asphaltene inhibitor had failed to improve the production. The
well was positioned in one of the better areas of the reservoir
and therefore was being scheduled for side-tracking and re-
completion to a single tubing string. Under these conditions
the well was considered ideal for a pilot test, the cost for the
intervention was considered to be the commercial risk in the
trial.
The produced oil has a GOR of 370 scm/m3 and the
reservoir is being produced at pressure above the bubble point;
the reservoir fluids also contain 2% H2S in the gas phase. The
reservoir properties are given in Table 3, along with the
completion design. Samples of asphaltene had been taken
from the long string and the composition analyzed (Table 1).
The composition was lower in asphaltene and higher in
formation fines than typically found in the field, but this
sample had been taken from the long string, which was shut-
in. This analysis had been completed 2 years earlier. New
laboratory tests were carried out with fresh samples just before
the treatment to confirm the suitability and effectiveness of the
new emulsion in dissolving and dispersing asphaltenes present
at the bottom of the well.
On this pilot treatment, the design philosophy was simply
to pump the maximum capacity of solvent that could be safely
handled and stored on the well site (Fig. 7). Solvent storage
volume available was 150 m3, which when diluted with the
water and additives, resulted in an available fluid volume of
450 m3, almost 10 times more than the volume used in
previous treatments. The treatment proposed was first to
ensure that the tubing and immediate perforations were
cleaned using a combination of bullheading (direct injection
through the completion) and washing with a coiled tubing and
jetting nozzle. Once these had been cleaned, the remaining
fluid volume would be pumped by bullheading at a rate below
the fracturing wellhead pressure and the wellhead limitation of
5,000 psi using co-mingled nitrogen to clean up the well
quickly. Consideration was given to using an asphaltene
inhibitor as the last stage of the treatment; however, in the
final treatment design this was decided against to verify the
longevity of the post-treatment production gains and compare
the results to treatment results where inhibitors had been used.
To measure the success of the treatment, target production was
established at the original level before the last severe damage
occurred. A short production history for the short string on the
well is in Fig. 8, showing (1) the typical rapid decline
associated with asphaltene plugging and (2) the failure of the
two earlier treatments to re-establish previous production
levels.
This first operation had to be completed during the spring,
and becaused we had not sourced a suitable high-flash point
solvent at this time a xylene-based solvent was used.
Execution of the Treatment
The treatment was performed over a 2-day period working
only during the daylight hours. An outline of the operational
sequence is as follows:
• Bullhead into the tubing with 25 m3 of emulsion and
allow to soak, while preparing to RIH with the CT. A
spacer of 5 m3 diesel was pumped to reduce the contact
between the wellhead and the aggressive solvent.
• Ran in the hole with a 1-1/2-in. CT down to 3200 m (MD)
pumping emulsion time by time. Further descent to the
lower perforations could not be achieved because of
excessive and unexpected overpull and the limited pull
capacity of the coiled tubing. This situation remained
unchanged even after pumping 6 m3 of emulsion (plus 1.0
SPE 101022
m3 of diesel for protection) through the CT-tubing
annulus.
• Pulled out of the hole with the CT while lifting the well
with nitrogen and put the well on production for cleanup.
Very soon, a dirty fluid arrived at surface, causing
problems to the surface facilities; suction of the oil-
transferring pumps of the Long Production Test (LPT)
plant became plugged by suspended asphaltenes. Some
defoamer was added downstream of the choke to assist
with the separation of the fluid in the field separator.
• Attempted further washing of the tubing to reach the
lower perforations with some pure solvent (xylene) and 4
m3 of emulsion pumped through CT without success; a
further unsuccessful attempt to reach the lower
perforations was made by spotting 4 m3 of acid before
pulling out of the hole with the CT after displacement of
the acid with the emulsion and finally by displacing the
CT volume to water.
• Bullheaded through the completion tubing 180 m3 of
emulsion at an average rate of 5.9 bbl/min; during this
period the treating pressure made a steady increase from
756 psi to 2,032 psi.
• Continued to bullhead 210 m3 more (390 m3 in total)
emulsion at 5.9 bbl/min with nitrogen added. Started at a
rate of 500 scf/min and increased after 50 m3 emulsion to
1,000 scf/min and then further increased to 1,500 scf/min
until the 170 m3 of emulsion had been pumped. The last
40 m3 was pumped without N2.
• Displaced with 1 m3 of diesel as a spacer. Final pumping
pressure at 5.9 bbl/min was 2,700 psi.
• The well was then left shut-in for 7 hours overnight and
opened to flow to a test separator, and immediately started
to unload the treating fluid.
It can be seen from the above data and Fig. 7 that when
performing the treatment there was an increase in the injection
pressure much higher than expected immediately after the
solvent started to enter the formation. This might relate to the
peak pressure that had been seen in the core testing, which
was believed to be caused by the swelling of the asphaltene, or
the increase in fluid viscosity effect when the emulsion was
absorbing the deposits. This effect would also contribute to
diverting the fluid across the intervals. A similar pressure
increase was recently recorded while treating a horizontal well
in the same area, despite the presence of several fractured
intervals along the open hole. This pressure increase occurred
once a wellbore volume was pumped, meaning the fluid was
treating the entire profile as a consequence of the diversion
given by swollen and dispersed asphaltenes.
Production Results
Following bullheading and displacement with nitrogen the
well flowed without lifting and initially was producing a very
heavy, viscous fluid. Leaving the sample static this viscous
fluid sample returned to a water-like viscosity after a few
hours at the surface. However, this heavy residue that was
being produced caused some surface equipment problems.
There was also some foaming occurring, to prevent this
becoming a problem in the separator an injection line was
9
fitted in the flowback line before the separator and a suitable
defoamer was injected.
After cleanup the final production of the well was close to
the original one before the severe plugging had occurred.
Because the well was not washed to the TD of the perforations
the production is also likely only coming from the upper
interval. Considering the lack of communication with the
whole perforated interval, the initial production target was
considered achieved or even exceeded.
The production decline after the treatment is following the
similar trend observed in May 2004, although this trend has
been delayed. This indicates that there is a presence of very
deep damage in the natural fracture system and the need for
further cleaning, possibly using a larger volume of emulsion.
It is impossible to remove this type of damage using the low
volumes of solvent employed in the earlier work and which
was typical of a standard treatment in the field.
The planned second treatment was never pumped in this
well because of the absence of authorization to continue the
Long Production Test. The cumulative oil produced by the
well after the job was enough to pay back the treatment in a
very short period of time.
This field trial proved that the emulsion was effective in
removing asphaltene deposits at the bottom of the hole and
into the fracture network. This justified a decision to treat the
first horizontal well in the same area with the emulsion.
Case Study 2
Well Description and Treatment Design
This case-study well is producing from a 6 ¼-in. ID casing
in a horizontal hole over 1000 m long, in the same reservoir as
the Case-1 well. The exceptional production capacity of the
Case-2 well was reduced by the presence of agglomerates of
asphaltenes that arrived on surface. These agglomerates
caused the choke to be plugged with an increasing frequency,
up to several times per day. To reduce the impact on the
production from the well, the fixed choke was replaced by a
manned choke manifold. This did not avoid the problem and
only minimized the production loss with an increased
operative costs.
An intervention to clean the tubulars and wellbore was
deemed necessary in the effort to maintain stable production
without repeated interruptions. The fluctuations in pressure
and rate are also known to have adverse effects on the
productivity of the wells. These fluctuations induce damage to
the fracture network by accelerating asphaltene deposition and
promoting formation debris movement along the horizontal
section, The debris is then transported toward the surface by
the oil stream, exacerbating the consequential plugging of the
choke by solids dispersed in the mass of asphaltenes.
The tubing was cleaned previously, in a separate operation
using a CT unit, in the effort to stabilize the production
parameters, by cleaning only the tubular section. This had the
contrary effect and the well started to have more problems.
This result has been later observed in several occasions in
other wells and possible explanations could be given.
The well was completed with a 4 ½-in. OD tubing on July
2001; 387 m of 4 ½-in. OD slotted liner was installed at the
bottom of the tubing to stabilize the extremely fractured
10
formation at casing shoe. The well is producing from a long
horizontal section: two zones are widely fractured, as shown
by mud losses recorded while drilling, and several other
fractured zones are known to exist in the producing interval,
making this well one of the most prolific in the area. The
sequence for the intervention was to initially wash the tubing
and fill the wellbore by bullheading the resultant emulsion.
This was considered to be effective because high achievable
injection rates in excess of 20 bbl/min were anticipated.
Coiled tubing was then to be used to wash over all the
producing intervals in the open hole by jetting with the
emulsion.
The emulsion was tested with a suitable asphaltene sample
from the well to be treated. In this case we had sourced a
heavy aromatic solvent (HAN) as areplacement for the xylene.
Treatment Execution
The treatment was performed over a 2-day period, working
24 hours. An outline of the operational sequence follows:
• 80 m3 of emulsion pumped, bullheading at 20 bbl/min
with N2 at 2,000 scf/min (about 3,700 psi WHP at the end
of this stage) and 20 m3 pumped without N2 to stabilize
the WHP during shut-in (3,450 psi at the end of
pumping).
• 2 hours shut-in (315 psi at the end of the shut-in) to give
time for the system to dissolve asphaltenes and disperse
agglomerates.
• 50 m3 of emulsion pumped by bullheading to renew the
solvent in the wellbore (3,370 psi of WHP at the end of
pumping, just before stopping pumps).
• RIH with the CT to maximum producing depth (i.e. depth
beyond which no mud losses were detected while drilling
and no evidence of fracture from logs) while pumping the
emulsion at 1.0 to1.5 bbl/min, reciprocating the coil at the
most interesting depths. Pumped 225 m3 of emulsion
through CT in more than 20 hours while washing the
horizontal section.
• The well was put on production by bullheading N2 (one
tubing volume) and opening the valve to the flowline.
When the CT tools were inspected following the operation
they were completely clean with no asphaltene deposits
sticking to the tool. Fig. 9 shows the tools at surface; compare
to Fig.1, which was from an earlier treatment on this well.
Results
The well started to produce oil immediately and it was
placed on production with no blockages from debris returning
to the surface (Fig. 10). There was a doubling of the
production before the treatment since it was possible to open
the choke without problems caused by the arrival of formation
debris at surface. This is considered to be a very successful
treatment and further treatments of similar are being planned
on the well at regular intervals, to prevent a reoccurrence of
the problem.
Conclusions
• Water-solvent emulsion systems have proven effective in
removing asphaltene deposits from oil wells that
SPE 101022
previously showed limited production benefit from
solvent-only treatments. In addition, emulsion systems are
seen as beneficial to the process because they leave the
pipe and possibly the formation in a water-wet condition;
a water-wet condition delays the onset of asphaltene
plugging once the well is placed back in production.
• The use of high ratios of water (60%) in the emulsion
allows larger treatments (200% more) to be performed
when solvent tank capacity is limited. The emulsion being
prepared by continuous mixing also has proven effective
in minimizing flammable-fluid storage capacity and
permits flexibility in the operations on the well site, with
an overall reduction in cost.
• The reduced amount of active solvent in the emulsion did
not influence the effectiveness of the treatment. Applying
an asphaltene removal treatment using solvents/emulsions
can be comparable to the use of acid in a sandstone
formation. The capacity of the emulsion to dissolve 300
grams of asphaltene per liter of fluid was seen to be more
than adequate for successful removal in the formation.
• An increase in injection pressure during injection of the
emulsion into the formation has been seen both in the
laboratory and during well treatments. The authors
propose that this increased injection pressure is from a
combination of the increase in viscosity of the emulsion
as it dissolves the asphaltene and also from the swelling
of the asphaltene coating on the formation during the
removal process.
• Increased injection pressure during the removal process is
seen as beneficial to the treatment because it assists with
diversion of the fluid when the maximum-rate diversion
technique is being used during the bullheading phase of
the treatment. This is only beneficial if this higher-
viscosity fluid is returned from the formation when the
well is placed on production, and this has proven to be the
case in the wells treated.
• Large amounts of dispersed, undissolved (or even
partially dissolved) asphaltenes have been detected on
every treatment in the returned fluid. Caution should be
exercised in using the emulsion if there is a concern that
this solid or semisolid and deformable material might
plug the pore throats of the formation, for example in
certain sandstone formations.
• Recent evidence indicates that the wells should be treated
routinely without waiting for the first signal of damage at
surface: deposition could be so severe at this point that
more than one treatment might be necessary to restore
productivity, making the volume required for one job
unmanageable.
• Further work needs to be done to optimize the treatment
with regard to the fluid volumes used and if water flushes
containing surfactants and or the use of inhibitors in
combination with the emulsion system will be useful.
• There are significant benefits in using an emulsion in
combination with a high-flash point solvent (HAN) from
the logistical and safety issues of pumping the treatment
on the well site.
SPE 101022
Appendix A—Solubility Testing
The asphaltene-solubility test is used to determine which
solvent solution dissolves the most asphaltene.
1. Prepare 100 mL of the desired solvent blend.
2. Place the blend in a flask.
3. Add weighted asphaltene sample and tightly seal the top
of the flask.
4. Vigorously shake the jar by hand for 10 seconds.
5. Place the jar in a water bath heated to the test temperature
50 to 70° C and leave static.
6. Weigh a Whatman® No. 50 (2.7 um) filter paper disc.
7. Place the filter paper disc inside the Buchner Funnel.
8. Using a Filtervac seal, insert the Buchner Funnel into the
sidearm vacuum flask.
9. Using the vacuum hose, attach the sidearm vacuum flask
to either the vacuum pump or faucet aspirator.
10. After 1 hour, remove the flask from the heated water
bath.
11. Activate the vacuum.
12. Open the flask and pour the contents onto the pre-
weighed filter paper disc.
13. Rinse the solids on the filter paper with alternating stages
of water and IPA.
14. Remove the filter paper.
15. Place the filter paper in an ambient temperature vacuum
oven.
16. After the solids are dry, weight the filter paper and solids
to determine an exact amount of sludge.
Data Interpretation: Calculate the percentage of asphaltene
dissolved with Eq. 1:
Percent (Final weight – Filter paper weight)
asphaltene = 100 – 100 ×
dissolved Initial weight of the sample
………………………………………………………………(1)
Nomenclature
HAN =Heavy Aromatic Solvent in the context a solvent with a
high-flash point temperature.
Acknowledgement
The authors thank their colleagues who have been involved in
these operations and the development and testing of the
products for their support and collaboration. We also
acknowledge the work that was done in Halliburton’s
European research centre by M. Rietjens and P. Steenbergen
in some earlier studies into asphaltene deposition. Finally, the
authors thank the management of Eni SpA, Shell and
Halliburton for their permission to publish this paper.
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11
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Ali D.: “A Simplified Method to Predict and Prevent
Asphaltene Deposition in Oilwell Tubing: Field Case,”
SPEPF (May 2005) 126.
15. Galoppini, M. and Tambini, M.: “ Asphaltene
“Deposition Monitoring and Removal Treatments: An
Experience in Ultra Deep Wells,” paper SPE 27622
presented at the 1994 SPE European Production
Operations Conference and Exhibition, Aberdeen, United
Kingdom 15-17 March.
16. Minssieux, Louis: “Removal of Asphalt Deposits by
Cosolvent Squeeze Mechanisms and Screening,” SPEJ
(March 2001) 39.
17. Howard, G.J.: “Adsorption of Polymers on Solids From
Apolar Media,” Interfacial Phenomena in Apolar Media,
H.F.Eicke and G.D.Parfitt (eds.), Marcel Dekker, Inc.
New York and Basel (1987).
18. Cimimo, R., Correra, S., and Bianco, A.D.: “Solubility
and Phase Behavior of Asphaltenes in Hydrocarbon
12 SPE 101022

Media,” Asphaltenes: Fundamentals and Applications,

Sheu. E. Y. and Mullins, O.C. (eds.)
19. Speight, J.G. and Moschopedis, S.E.: “On the Molecular
Nature of Petroleum Asphaltenes,” Chemistry of
Asphaltenes, by J.W.Bunger and N.C.Li, Advances in
Chemical Series 195, 1981.
20. Edwards, D.A., Luthy, R.G., and Liu, Z.:, “Solubilization
of Polycyclic Aromatic Hydrocarbons in Micellar Non-
ionic Surfactant Solutions,” Envir.Sci.Technol. 25 (1991)
127.
21. McAuliffe, C.D.: “Oil-in-Water Emulsions and Their
Flow Properties in Porous Media,” JPT (June 1973) 727.
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in Porous Media,” Emulsions: Fundamentals and
applications in the petroleum industry, L.L. Schramm
(ed.), Advances in Chemical Series 231, (1992)
Washington, DC, Chap. 6, 219.
SPE 101022 13

TABLE 1—ANALYSIS OF THE DEPOSITS FROM SEVERAL SOURCES

Downhole Surface Case Study 1* Downhole
Asphaltene Sample Vessel Asphaltene Sample
Paraffin/heavy hydrocarbon residue (% w/w) 33.0 61.1 54.0 65.5
Asphaltene content (% w/w) 66.9 20.6 25.0 34.4
Fines content/toluene insolubles (% w/w) 1.0 18.3 4.0 0.1
Water content (% w/w) – – 17.0 –
Melting point range (°C) +/- 120-180 +/- 70-80 Not determined 99.0
*Sample taken from the long string of the well.

TABLE 2—SCREENING TESTS FOR SOLVENT PRODUCTS

Solvent Type Flash Point (°C) Lab Test (%)

Xylene plus 10 to 30% Ethyl benzene 27 100
Terpene hydrocarbon byproducts plus 10 to 30% Isopropenyl, 1-methylcyclohexen 35 Not Tested
Terpenes and terpenoids, turpentine-oil limonene, fraction 54 99.69
Heavy aromatic petroleum naphtha plus 5 to 10% 1,2,4 Trimethylbenzene 63 100
Naphtha, hydotreated heavy 68 0
Note: Testing determined that the following solvents could be employed to dissolve a typical downhole deposit.

TABLE 3—WELL AND RESERVOIR DATA CASE STUDY 1

Perforated depth 3539 m to 3790 m

Interval gross height 251 m
Interval net height 118 m
Packer depth 3244 m
2-7/8 in. to 3252 m
Tubing
2-3/8 in. to 3794 m
3
Capacity wellbore to perforations 14.6 m
Casing 9-5/8 in. to 3430 m
Liner 7-in., 32 lb/ft 3271 to 3815 m
Bottomhole temperature 90.5 °C
2
Reservoir pressure 321 kg/cm
Note: Dual completion information is for the short string through which the treatment was
completed
14 SPE 101022

Fig.1—Tools extracted from the well (Case Study 2) shows asphaltene accumulation in the coiled-tubing riser and on the CT tools.

Fig. 2—Capacity of solvent to dissolve deposits.

SPE 101022 15

Fig. 3—Dispersion of deposit in water and surfactant.

Fig. 4— Residue left on the filter: (1) South Italy – 1 gram/100 mL; (2) North Italy – 1 gram/100 mL; (3) South Italy - 5 gram/100mL; (4) 100%
Xylene – 1 gram/100mL.
16 SPE 101022

Fig. 5—Residue left on the filter by the novel emulsion.

SPE 101022 17

Fig. 6—Equipment layout at the well site.

18 SPE 101022

Fig. 7—Treatment data during solvent injection.

Fig. 8—Production data from Well Case 1.

SPE 101022 19

Fig. 9—Coiled tubing following an emulsion treatment.

Fig. 10—Production data from Well Case 2.