Development and Field Use of a Novel
Solvent/Water Emulsion for the Removal
of Asphaltene Deposits in Fractured
Carbonate Formations
Stephen Lightford, Halliburton; E. Pitoni, Eni SpA; F. Armesi, Halliburton; and L. Mauri, Eni E&P
Summary
The formation of asphaltene scale inside the tubing or in the res-
ervoir is a common problem associated with crude oils in many
parts of Italy and is common to the industry as whole. In Italy,
regular treatments with coiled tubing or washing by bullheading
are performed to re-establish production. While asphaltene inhibi-
tors can be injected into the tubing string, asphaltenes can still
create problems below the injection point and plug the perfora-
tions, 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 effec-
tive 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 redeposition of the asphal-
tene in the formation and increases the rate of the production
decline, increasing the frequency of remedial treatments.
This paper describes the laboratory development and field ap-
plication of a water/aromatic-solvent emulsion system that has
been used successfully 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 remov-
ing asphaltene deposits, when compared to alternative solvents that
have been used. This is of particular significance to those wells
where large volumes of a washing phase have to be pumped down-
hole. Hazards also have 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 southern Italy will be dis-
cussed, describing the placement technique used 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 pro-
duction was almost 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 previ-
ous 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 compo-
Copyright 2008 Society of Petroleum Engineers
This paper (SPE 101022) was accepted for presentation at the 2006 SPE Annual Technical
Conference and Exhibition held in San Antonio, Texas, 2427 September 2006, and revised
for publication. Original manuscript received for review 27 December 2006. Revised manu-
script received for review 30 April 2007. Paper peer approved 7 November 2007.
August 2008 SPE Production & Operations
nents of petroleum. These compounds occur in many crude oils in
the form of colloidal, suspended, solid particles. They are charac-
terized by their insolubility in light paraffin hydrocarbon solvents,
such as pentane or petroleum ether. Chemically, the asphaltene
fraction of petroleum is composed of polycyclic, condensed, aro-
matic rings with several side chains. These compounds have rela-
tively high molecular weights and are considered polar materials
because atoms of sulfur, 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 normally are 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 sur-
faces. 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
(e.g., along a flowline collecting oil from different wells/
reservoirs). To compound the problem further, emulsions can be
stabilized by asphaltenes. 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, as in the case
of the wells discussed in this paper where the deposits are fre-
quently a combination of asphaltene and paraffin, often associated
with inorganic material such as formation solids, salts, and
iron oxides.
The variable nature of the asphaltene problems is caused by
reservoir conditions and chemistry of the oil. Intervention-
treatment design and timing is based generally 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 deter-
mine the timing and the method of the intervention. The same
practices, however, were no longer achieving the success of the
past, and the severity of the problem was increasing with the age
of the field. To improve 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 dif-
ferent 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 work (Dubey and Waxman 1991;
Crocker and Marchin 1988; Gonzlez and Moreira 1991; Gonzlez
and Travalloni-Louvisse 1993; Acevedo et al. 1995; Dean and
McAtee 1986; Piro et al. 1996) has been conducted to further
301
understanding of the mechanism and chemistry of asphaltene floc-
culation, deposition, and adherence to surfaces. The modern un-
derstanding of the deposition process can be summarized as follows:
The asphaltene-deposition process is controlled by the ther-
modynamics of the system (Leaontaritis et al. 1994); only when
these conditions change can flocculation and deposition of the
asphaltene occur.
Crude oils contain asphaltene and polar elements (lower mo-
lecular-weight resins) that are deposited onto the rock surface in a
manner that follows a Langmuir-1 or -2 type curve, which are
characterized by a steep slope at very low concentrations (Giles
1981) and a point of stability reached quickly. Research has shown
that this deposition can continue at a much slower rate and does
not stabilize (Piro et al. 1996). The resins also adsorb on the rock
or tubulars, but not as strongly as the larger asphaltenes (Gonzlez
and Travalloni-Louvisse 1993).
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 (Crocker and Marchin 1988) by
penetrating the connate-water film and replacing the water at ac-
tive sites on the rock surface (Hall et al. 1983).
The presence of water also affects the adsorption process.
Experiments on water-wet rock show a considerable reduction in
adsorbed asphaltenes (Dubey and Waxman 1991; Crocker and
Marchin 1988; Buckley et al. 1997; Trbovich and King 1991).
It has been shown that asphaltenes can precipitate in the
formation, resulting in pore plugging (Piro et al. 1996), but this
occurs close to the point of destabilization, hence the damage zone
is likely to be quite small (Kocabas 2003); however, if the depo-
sition is likely to be high, severe core plugging occurs in a rela-
tively short time frame.
Paraffin separates from crude oils when the temperature of
the oil cools sufficiently. Fine particles including asphaltenes act
as nuclei for the crystallization of the small wax particles sus-
pended in the oil. This mechanism can create paraffin deposition in
conditions under which this might not occur normally.
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 are producing the well with the aim of
eliminating the thermodynamic conditions that cause the floccu-
lation and/or modifying 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 temperature and pressure drop, causing the
deposition of the heavier organic compounds (Leaontaritis et al.
1994; Alkafeef et al. 2005). Pressure has little or no direct effect on
increasing the solubility of the heavier organics in crude oil; how-
ever, it holds dissolved gases and volatile constituents in solution.
Pressure assists in maintaining the asphaltenes in solution at for-
mation temperature.
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 decreased by reducing the fluid pressure to
the bubblepoint. 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 bubblepoint, light paraf-
fin 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 con-
302
tent; hence, asphaltene deposits can occur in each area, leading to
plugging and loss of production.
Under ideal conditions, the well should be produced at a pro-
duction rate such that the flocculation and deposition will not
occur (Leaontaritis et al. 1994; Galoppini 1994). In managing the
reservoir, the issue becomes one of balancing the production con-
ditions and production rate with one that will reduce the produc-
tion 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 pres-
sure and flow and the trend of the decline is important; generally,
however, once this effect is seen in the surface data, a rapid pro-
duction decline will occur that can result in the loss of the entire
production from the well until an intervention is performed. Proper
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 frac-
tured 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 accumu-
lation of deposits are oily coatings, surface roughness, and elec-
trically chargeable materials. All these exist in the formation ma-
trix and tubulars. Water-wet surfaces have a lesser tendency for the
deposition of asphaltenes; asphaltene inhibitors also can 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 (Piro
et al. 1996). For the inhibitor or water-wetting agent to be effective
in delaying the redisposition, it must first adhere to the surface,
which 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.
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 in-
hibitors also has been a common practice. These have been placed
in the solvent or as an overflush in an attempt to delay the depo-
sition on the formation in the lower wellbore by their slow de-
sorption and backproduction 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
be cleaned only partially. Cleaning should, however, be as com-
plete as possible, and the key to a successful treatment lies in 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 as-
phaltene 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. On the basis of internal core-test studies and pre-
vious work, the following factors are all considered to be keys to
a successful, long-lasting removal treatment:
Deposits have different solubility in different solvents, de-
pending on the type of asphaltene in the crude (Minssieux 2001).
Cosolvents can be added to the solvent to improve the efficiency
of dissolution of the asphaltene, and generally they will also im-
August 2008 SPE Production & Operations
prove the desorption from the formation surface; therefore, cosol- surface of the tubulars, as was illustrated by the condition of the
vents serve two beneficial purposes in the removal process. coiled-tubing (CT) equipment pulled out of the well after several
Though it might be possible to remove/desorb the asphaltene, interventions. Fig. 1 shows the condition of the CT tools as a
in the wrong environment, it will be readsorbed immediately onto consequence of the accumulation of asphaltenes inside the riser
the formation or rock, either during the removal process or when during a well-washing operation.
placing the well on production. To prevent the readsorption, these There was evidence from the production declines and from
polar sites need to be occupied by other polar chemicals that have the failure of the solvent treatments to re-establish previous pro-
a greater affinity for the rock surface; asphaltene inhibitors and/or duction levels in some wells that the deposition of asphaltene was
water can be used for this purpose. occurring deep in the natural-fracture system inside the formation.
Because asphaltenes have a higher affinity to adsorb onto The depth and extent of this damage was difficult to determine;
surfaces with a similar structure [i.e., that is, on core surfaces with however, it was envisaged that much larger volumes of solvent per
adsorbed asphaltenes (Acevedo et al. 1995)], cleanup of asphal- m of interval were needed to penetrate deeper into the natural-
tene-damaged wells should be as thorough as possible. Simple fracture system.
solvent treatments, with toluene for example, are usually not very A constraint on the review was that to perform this work
effective because their effect lasts for a few days/weeks only. quickly, the testing needed to be performed predominantly in a
Treatments with a water-based fluid are much more promising and field laboratory with limited resources; thus, the test method
are reported to remain effective over several months (Howard 1987). and measurement of the performance of the products needed to
To dissolve and remove the asphaltene from the rock/pipe be simple.
surface requires a strong polar solvent that not only takes the
asphaltene into solution but also breaks the molecular bond of the Issues Related to Sample Source. The first issue to be addressed
asphaltene that retains it to the surface of the formation. Experi- in the laboratory was the selection of the samples to be used to
ments have shown that cleanup with pure toluene removes most of evaluate the solvents and cosolvents. Asphaltene samples used in
the asphaltene fraction, but the surface will still be covered with the laboratory are generally prepared by mixing a crude oil with an
asphaltenes (Cimimo et al. 1996; Speight and Moschopedis 1982). aliphatic hydrocarbon such as n-hexane. The composition of the
The remaining asphaltenes are likely to be the most-polar and precipitated asphaltenes can be varied by using a lighter alkane or
highest-molecular-weight fraction. As a consequence, the core sur- heavier alkanes. In propane, for example, asphaltenes, resins, and
face will still be intermediate- to oil-wet. Because an asphaltene- other heavy hydrocarbons precipitate; while in decane, the
covered surface is more prone to redeposit of asphaltenes (Buckley harder asphaltenes, but few resins, precipitate (Gonzlez and
et al. 1997), cleanup should be as efficient as possible. Travalloni-Louvisse 1993). Regardless of that, the composition of
Besides film formation, the presence of water can be benefi- the deposits in the well will most likely be different from those
cial since it can compete with asphaltenes for active sites on the produced in the laboratory (Speight and Moschopedis 1982), with
rock surface; however, from the literature and from in-house ex- downhole asphaltene samples normally containing a much higher
periments, desorption of asphaltenes cannot be achieved fully. In fraction of the more-polar, insoluble asphaltenes. Solvents that are
other words, the rock surface can be changed to intermediate-wet regularly applied in the field, such as toluene and xylene, will
at best. usually dissolve only 50% of a typical downhole sample. In addi-
It has been demonstrated that the wettability of a core can be tion, the deposits in the wellbore typically are not only asphaltenic,
changed from water-wet to oil-wet by a Dean-Stark extraction but also comprise other organic or inorganic deposits and water.
because toluene strips the water off the formation-core surface
(Dubey and Waxman 1991).
Effective plugging can occur because of mechanical plug-
ging, 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 manner
similar to a well that has been damaged by mobilized forma-
tion fines).
Treating the surface of the rock and tubulars requires a well
intervention and injection of solvents to remove the adhering as-
phaltene 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 proved to be difficult or im-
possible in laboratory conditions; so, given the more complex
nature of a wellbore and the inefficiencies involved in fluid diver-
sion 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 only a question
of selecting the most effective and strongest solvent, but also the
surface coated with the deposits should be left such that the next
deposition process is delayed. This can be achieved if the maxi-
mum possible amount of the asphaltene coating is removed from
the surface and the surface 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
southern Italy were becoming less effective and shorter lasting
than in the past. To try to improve the design of the intervention,
it was decided that a detailed review of the current solvent being
used should be made for several specific reasons:
Improve the solvency capacity of the solvent routinely being
used, thus improving the cleanup efficiency.
The dissolved asphaltene, while still in the solvent used for Fig. 1Tools extracted from the well (Case 2) show asphaltene
the treatment, was being immediately readsorbed onto the metal accumulation in the CT riser and on the CT tools.

August 2008 SPE Production & Operations 303

 On the basis of these factors, downhole samples are preferred
and the results using laboratory-prepared samples might be unrep-
resentative of the deposit in the well. There are difficulties in
obtaining sufficient samples of the materials from the well for
comparative testing purposes. In addition, downhole samples from
one well are likely to be different from samples collected in an-
other 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. An ideal situation would be to have
a sample from each source; however, they are difficult to obtain.
Therefore, a compromise needs to be reached and in this work, it
was decided that the following procedures would be implemented:
Samples taken from surface separators and surface lines
would be used for intial testing and screening of solvents.
When available, samples from the well to be treated would be
checked with the standard composition of emulsion to confirm
its suitability.
Selected analysis of the asphaltene sample was also performed
to determine the amount of asphaltene, paraffin, and other organic
and inorganic material in the sample and to compare this with
other sources. A typical analysis of sample from southern 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 labo-
ratory; therefore, there was confidence that it would be successful
in removing the apshaltene deposits in the well or formation.
Solvent Selection
General. A number of theoretical methods exist to determine the
optimum solvent for a particular asphaltene [Kauri-butanol num-
ber, Hildebrand solubility parameter (Minssieux 2001), and
Hansen solubility parameter]. The variable composition of asphal-
tene 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 well 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 cosolvents (highly polar solvent) was made to determine wheth-
er the residue could be reduced further. The approach taken is
summarized as follows:
Test the solvent currently being used with the field sample,
then test with toluene and compare the results; this method was
used because it has the highest Kauri-butanol rating of the com-
mon solvents, so it provided a base line to compare results.
Add a cosolvent to the solvent in use in the field to determine
whether this addition could improve the result, then optimize the
concentration of the cosolvent.
Repeat the tests using higher-flash-point solvents to arrive
at a suitable solvent/cosolvent system that has a sufficiently
high flash point to be used safely in the field with improved as-
phaltene solvency.
The test procedure, detailed in the Appendix, is based on a
standard company procedure. This procedure was modified to rep-
resent the conditions expected with 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.
304
ResultsSolvent-Only Testing. Testing quickly established that
with the downhole samples, a large amount of residue was remain-
ing after using the current solvent, a wash oil comprising distillates
(coal tar), naphthalene oils, and methylnaphthalene fraction
(OLG). A pyrrolidone cosolvent was then used in conjunction with
solvents; it was found that the cosolvent improved the performance
of the base solvent. The residue diminished from 24% to approxi-
mately 2%. Toluene resulted in less residue (6%), without the use
of a cosolvent; this was expected. When adding the cosolvent,
however, the residue was reduced further to a negligible amount.
Downhole and surface samples were tested with similar results
(Fig. 2). On the basis of the successful initial laboratory tests with
the cosolvent, it was decided not to evaluate further cosolvents.
Although the solubility was comparable between the xylene added
with cosolvent and the OLG, the appearance of the samples was
vastly different. The xylene/cosolvent had only a small amount of
adherence to the glassware used in the testing, while the OLG had
a strong affinity and left sticky deposits that were difficult to clean.
This was not a problem seen only in the laboratory; field work had
also indicated that this was reducing the effectiveness of the treat-
ment. There was clear evidence from the condition of the down-
hole 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-polarity fractions of the
asphaltene, while being dissolved 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 tool
strings being used, it could be surmised that this was also occurring
in the tubulars and in the formation. Moreover, OLG was consid-
ered unsuitable for well treatments because of the foreseeable use
of acid in some of the treatments; OLG is acid-sensitive because it
contains components that are precipitated by hydrochloric acid,
making the residual solvent ineffective and making the acid par-
tially 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 imme-
diate deposition of the asphaltene was thought to be the key to
improving 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 5C is used. The OLG solvent currently used had a
flash point of 90C, so it could be stored safely in standard tanks
with suitable valve material. Because of the large-volume treat-
ments being planned, toluene (flash point of 6C), while being the
best-performing solvent in the laboratory, was seen to be too haz-
ardous for use in the field. A similar situation also applied to the
use of xylene (flash point of 28C), which could be used during the
cold winter and cool spring months, by using inert blankets on the
tanks to enable safe storage and pumping; this procedure would
not be acceptable in the summer, when the ambient temperatures
are above 30C.
August 2008 SPE Production & Operations
 Fig. 2Capacity of solvent to dissolve deposits.
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 the solvency power of the base solvent, decreased the
flash point, or were potentially damaging to the refinery catalyst
(e.g., chlorine-based compounds).
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 greater than 55C
was considered suitable and was tested using field samples from
southern Italy. Eventually, a higher-flash-point (66C), heavy aro-
matic naptha solvent was found that yielded results similar to the
xylene (listed as the Solvent 3 in Table 2). The locally available
solvent was, however, contaminated with 10% 1-methoxy-2-
propanol acetate; this contaminant was found to be compatible
with the refinery catalyst and has a higher flash point than the base
solvent, and it 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 accom-
pany handling of contaminated tubing. Various well-washing sur-
factants (detergents) were being tested.
August 2008 SPE Production & Operations
It is well understood that the addition of surfactants (McAuliffe
1973) can be used to disperse organic deposits in the water phase
and assist in removing these deposits from surfaces. These re-
moved 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,
alkyl poly glucoside, that was particularly effective in breaking
down the samples of the deposits from the tubulars in the wells in
southern Italy. Fig. 3 shows the dispersed sample in the water
phase following heating. When washing tubing, the dispersion
processes are 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 forma-
tion, there is not enough 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 inject 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 allowing them to be dissolved quickly 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 with the emulsion gave a result that sur-
passed the solvent-only system. The emulsion was found to not be
305
 Fig. 3Dispersion of deposit in water and surfactant.

only as effective in dissolving the asphaltene as the base solvent,
but it appeared to do this more quickly and leave a much cleaner
residue (Fig. 4).
The appearance of the all laboratory equipment following dis-
solution of the deposits showed that it was water-wetting and there
was little to no adhesion of the dissolved asphaltene on the equip-
ment. 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 criterion of permitting
greater volumes to be used without needing to store 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-

Fig. 4Residue left on the filter, left to right: (1) southern Italy: 1 g/100 mL; (2) northern Italy: 1 g/100 mL; (3) southern Italy:
5 g/100mL; (4) 100% xylene: 1 g/100mL.

306 August 2008 SPE Production & Operations

wetting capability of the emulsion might delay the redeposition 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 into the formation.
Solubility parameters of the solvent phase are determined by
the type and amount of the organic solvent, cosolvent, surfac-
tant(s), and water content. This determines the amount of asphal-
tenes and other organic components in the deposits that can be
taken into solution. Depending 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, how-
ever, leads to the further question of how much solvent capacity is
required to treat a formation.
To determine whether the emulsion system would dissolve sig-
nificant amounts of solvent, a test was conducted with increased
amount of deposits; instead of using the standard 5 g per 100 mL
as in the standard test, 6 times this amount was added (30 g).
Extrapolating this volume to the well, it would relate to the re-
moval of 300 kg (approximately 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 dissolution of the deposits
confirms the systems solvency power and deposit-removal capac-
ity. While this is possible in the laboratory, the situation in the well
is somewhat different because some of the solvent will be ab-
sorbed 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. The aim of this
work, however, was to treat the formation better, 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%
hydrochloric acid is 220 kg/m3 of calcium carbonate, which, based
Fig. 5Residue left on the filter by the novel emulsion.
August 2008 SPE Production & Operations
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 more than
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 asphaltene-cleanup process is envisioned as
being similar to the process of damage removal in a sandstone
formation where the rock matrix is not dissolved but the plugging
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 with a 66% water/surfactant phase in combination
with a 34% organic (xylene) solvent and cosolvent 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 leav-
ing 24% residue (tested at 0.05 g/L only) using the same samples
(Fig. 5). The emulsion combined with the deposit was not exces-
sively 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. Exten-
sive coreflood testing in a sandstone core had been completed
previously in the evaluation of different solvent treatments; this
included some emulsions with 10% water. The cores used for the
testing had been damaged in the laboratory with asphaltene ex-
tracted from the crude oil that was injected into, then baked onto,
the core. Subsequently, solvents were injected into the core to
remove the damage. During injection, the effluent was monitored
for asphaltene, the regained permeability was tested, and the core
was 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 asphal-
tene was accomplished only when there was an initial increase in
the injection pressure. The researchers involved explained this
phenomenon as a process such that when the asphaltene adsorbs
307
the solvent into the organic coating, this adsorption causes the
coating to swell and reduces the effective pore diameter. There-
fore, 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 lead
to an increase in wellhead pressure (WHP) during injection of the
solvent is an increase in viscosity of the water phase. While the
asphaltene is taken into solution, the oil-in-water emulsion incor-
porates 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, as has been demonstrated both in wells and in the
laboratory; therefore, in general, emulsions should be avoided
(Soo and Radke 1984; Kokal et al. 1992; Edwards et al. 1991).
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 on 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
and not from the pore spaces in the formation; therefore, unless the
created emulsion was extremely viscous, it was felt that the for-
mation 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, it 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 WHP,
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 Wellsite. 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 proved
that the fluid 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 wellsite.
In addition, 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 be evaluated
only with a field trial.
Since the emulsion created is unstable and separates into two
phases in a matter of several 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 liq-
uids. To overcome this problem, it was decided that the best ap-
proach was to mix the emulsion continuously as it was pumped
downhole. The safest place to do the mixing was in the high-
pressure line immediately before the lines entered the wellhead. A
surface system arrangement as shown in Fig. 6 was used to com-
plete 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 being tanks for the storage of the
308
water, an in-line high-pressure mixer, and suitable liquid-additive-
injection pumps.
Using this mixing system creates less waste because tank bot-
toms are minimized, and if the operation is terminated early, the
base materials could be reused.
Case Histories
Case 1. A well constructed as a dual-tubing completion was cho-
sen for a pilot test because of the severe nature of the asphaltene
plugging in the well. Two previous remediation attempts with
solvent and asphaltene inhibitor had failed to improve production.
After the pilot treatment with the water/aromatic-solvent emulsion
system, the well produced enough additional hydrocarbon revenue
in 2 weeks to pay for the treatment.
Case 2. A horizontal hole more than 1000 m long, in the same
reservoir as in Case 1, had its exceptional production potential
reduced by agglomerates of asphaltenes being produced and car-
ried to the surface. These agglomerates caused the choke to be
plugged with an increasing frequency, up to several times each
day. Previous cleanout efforts had resulted in even worse plugging.
A treatment with the water/aromatic-solvent emulsion system
presented here 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
nitrogen, N2, at 2,000 scf/min (approximately 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-hour shut-in (315 psi at the end of the shut-in) to give time
to 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 WHP at the end of pumping, just
before stopping pumps).
Run in hole 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 emul-
sion at 1.0 to 1.5 bbl/min, reciprocating the coil at the most inter-
esting 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. 7 shows the tools at the surface; see Fig.1, which
shows tools from an earlier treatment on this well.
Conclusions
1. Water/solvent emulsion systems have proved effective in re-
moving asphaltene deposits from oil wells that previously
showed limited production benefit from solvent-only treat-
ments. In addition, emulsion systems are seen as beneficial to
the process because they leave the pipe and possibly the forma-
tion in a water-wet condition; a water-wet condition delays the
onset of asphaltene plugging once the well is placed back on
production.
2. 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 con-
tinuous mixing also has proved effective in minimizing flam-
mable-fluid storage capacity and permits flexibility in the op-
erations at the wellsite, with an overall reduction in cost.
3. The reduced amount of active solvent in the emulsion did not
influence the effectiveness of the treatment. Applying an asphal-
tene-removal treatment using solvents/emulsions can be com-
parable to the use of acid in a sandstone formation. The capacity
of the emulsion to dissolve 300 g of asphaltene per liter of
fluid was seen to be more than adequate for successful removal
in the formation.
4. An increase in injection pressure during injection of the emul-
sion 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 vis-
August 2008 SPE Production & Operations
 Fig. 6Equipment layout for treatment.
cosity of the emulsion as it dissolves the asphaltene and the
swelling of the asphaltene coating on the formation during the
removal process.
5. 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
beneficial only if this higher-viscosity fluid is returned from the
formation when the well is placed on production, and this has
proved to be the case in the wells treated.
6. Large volumes of dispersed, undissolved (or even partially dis-
solved) asphaltenes have been detected on every treatment in the
returned fluid. Caution should be exercised in using the emul-
sion if there is a concern that this solid or semisolid and de-
formable material might plug the pore throats of the formation
(e.g., in certain sandstone formations).
7. Recent evidence indicates that the wells should be treated rou-
tinely 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.
8. Further work is needed to (1) optimize fluid volumes in the
treatments, (2) assess water flushes containing surfactants, and
(3) determine whether use of inhibitors in combination with the
emulsion system is beneficial.
9. There are significant benefits in using an emulsion in combina-
tion with a high-flash-point solvent (heavy aromatic solvent)
August 2008 SPE Production & Operations
from the logistical and safety issues of pumping the treatment at
the wellsite. The authors believe this system is unique in using
an emulsion for the removal of asphaltene deposits from the
formation matrix.
Acknowledgments
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 performed in Halliburtons European research center by
M. Rietjens and P. Steenbergen in some earlier studies into as-
phaltene deposition. Finally, the authors thank the management of
Eni SpA, Shell, and Halliburton for their permission to publish
this paper.
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August 2008 SPE Production & Operations
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 seal the top of the
flask tightly.
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 70C) and leave static.
6. Weigh a Whatman No. 50 (2.7m) 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 the 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 preweighed
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, weigh the filter paper and solids to
determine an exact amount of sludge.
Data Interpretation: Calculate the percentage of asphaltene dis-
solved with Eq. 1:
Percent
Final weight Filter paper weight worked for the R&D department at a chemical company in
asphaltene = 100 100
dissolved Initial weight of the sample
. . . . . . . . . . . . . . . . . . . . . . . . (A-1)
SI Metric Conversion Factors
ft 3.048* E01 m
ft3 2.831 685 E02 m3
lbm 4.535 924 E01 kg
*Conversion factor is exact.
Stephen Lightford works for Halliburton as part of the European
Technology Team based in the UK. He provides technical sup-
port to projects in eastern hemisphere and is primarily involved
in the companys production optimization operations that
deal with sand control, stimulation, and completion tools.
Lightford has worked for Halliburton Services since 1980 in op-
erations in the Middle East, Africa, the North Sea, and Europe.
Before the current assignment, he was working as the Technol-
ogy Manager for Production Enhancement in Russia, leading a
group of engineers involved in well stimulation. Lightford holds
a BSc degree in mechanical engineering. Enzo Pitoni is the
Project Team Leader for Production Optimization in the ENI
SpA Italian district. In his current position, he is responsible for
the development of innovative solutions to improve the pro-
duction of oil and gas from existing or newly developed fields.
Before taking his current position, he worked as a global advi-
sor for production optimization, based in Milan, and was in-
volved in both Italian and international operations. He has also
worked and lived in Tunisia and the Middle East. His expertise
includes stimulation, water shutoff, and sand-control opera-
tions. He holds a PhD degree in chemistry from Perugia U., Italy,
and started his career working in the research department
there. Franco Armesi, deceased, was a Senior Scientist Labo-
ratory Supervisor for Halliburton Services, Italy, since 1986.
There, he developed procedures and led research projects in
production enhancement and cementing. Before that, he
Ireland. Armesi held a chemistry doctorate. Luca Mauri cur-
rently works for Production Optimization Technologies Depart-
ment of ENI Exploration & Production Division.

August 2008 SPE Production & Operations 311