SPE 107584
Relative Permeability Modifiers and Their Use in Acid Stimulation in HPHT
Low-Permeability Carbonate Formations: Offshore Mexico Cases
Eduardo Soriano Duverney, Fernando Robles, Halliburton; Antonio Inda Lopez, Octavio Steffani, PEMEX
Copyright 2007, Society of Petroleum Engineers
This paper was prepared for presentation at the 2007 SPE Latin American and Caribbean
Petroleum Engineering Conference held in Buenos Aires, Argentina, 15–18 April 2007.
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Abstract
Successful acid stimulation requires a method for diverting an
acid across the entire hydrocarbon-producing zone. Because
most producing wells are not homogeneous and contain
sections of varying permeability, being able to completely
acidize the interval is a major problem. This paper describes
the use of a new low-viscosity system that uses a relative
permeability modifier (RPM) that diverts acid from high-
permeability zones to lower-permeability zones and inherently
reduces formation permeability to water with little effect on
hydrocarbon permeability. This system has been used
effectively offshore Mexico with success for more than two
years. The cases presented in this paper show the first
application in a low-permeability carbonate formation where
oil production was increased significantly compared to
previous traditional acid treatments using conventional
diverters.
The other important feature of this work is that the
downhole conditions were high-pressure/high-temperature
(HPHT). Details from the jobs using this new RPM acid-
diversion system will be presented showing pre- and post-job
production results.
Introduction
Matrix acidizing enhances well productivity by reducing the
skin factor. The skin factor can be reduced if near-wellbore
damage is removed or if a highly conductive structure is
superimposed onto the formation. In either case, the result is a
net increase in the productivity index, which can be used
either to increase the production rate or to decrease the
drawdown pressure differential. Although the benefits of an
increased production rate are evident, the benefits of reduced
drawdown are often overlooked. Decreased drawdown can
help prevent formation collapse in weak formations, reduce
water or gas coning, minimize both organic and mineral
scaling, and/or shift the phase equilibrium in the near-wellbore
zone toward smaller fractions of condensate or solution gas. A
reduced drawdown pressure can also help ensure that a greater
percentage of the completed interval contributes to
production.1
In attempts to achieve uniform placement of acid across all
layers, various placement techniques have been used.2 The
most reliable method uses mechanical isolation devices (such
as straddle packers) that allow injection into individual zones
one at a time until the entire interval is treated. However, this
technique is often not practical, cost-effective, or feasible.
Without a packer, some type of diverting agent must be used.
Typical diverting agents include ball sealers, degradable
particulates, viscous fluids, and foams. Although these agents
have been used successfully, all have potential disadvantages
and none address the problem of increased water production
that often follows acid treatments. Therefore, it would be a
major advantage to have a material that could inherently
decrease the formation permeability to water while also
providing diversion.
One method of controlling water production uses dilute
polymer solutions to decrease the effective permeability to
water more than to oil. These treatments may be referred to as
relative permeability modifiers (RPM), disproportionate-
permeability modifiers, or simply, bullhead treatments. The
latter name is so called because these treatments can be
bullheaded into the formation without the need for zonal
isolation. RPM systems are thought to perform by adsorption
onto the pore walls of the formation flow paths.3-5
Published reports have documented good results from
using RPMs for controlling water, either as a bullheaded
treatment in sandstone formations6-8 or as a preflush in
fracturing operations where highly water-saturated layers were
close to the fractured zone.9-11 Another paper has also
described the development of an RPM based on a
hydrophobically modified, water-soluble polymer (referred to
as an associative polymer, or AP).12 This group of polymers
was selected for study because their properties can be altered
in ways that render them valuable for oilfield applications. A
laboratory study of this polymer has also been the subject of a
paper, which detailed its use as an acid diverter in both
sandstone and carbonate lithology.13 In addition, field results
are already reported in which RPM technology has been used
with success in acid stimulation of carbonate formations
where hydrocarbon production has increased with no increase
2 SPE 107584
in water production, and in some cases a decrease in water
production.14
Associative Polymer Properties
The solution properties (such as rheology and viscosity) of
both ionic and nonionic, water-soluble polymers are uniquely
modified when hydrophobic groups are introduced into the
polymer chains.15,16 The primary factor responsible for the
property modification is the associative tendency between the
hydrophobic groups when placed in aqueous medium.
Previous testing has shown a unique shear thickening
phenomena for the AP used in the current work. However, the
solutions used in diversion operations show very low viscosity
(<2 cp) at surface conditions.13
The adsorption behavior of hydrophilic water-soluble
polymers can also be modified in a unique manner by the
introduction of hydrophobic groups. Rather than reaching a
plateau adsorption, as is common for hydrophilic polymers,
hydrophobic modification appears to produce a continued
growth in adsorption with increased polymer concentration.
This behavior is attributed to associative adsorption of
polymer chains on previously adsorbed layers of polymers.17
Viscosified, or foamed, fluids commonly used for acid
diversion can result in high friction pressure and require
special manifolding and/or pumping equipment. The low
viscosity of the AP diversion system results in ease of mixing,
low friction pressures, no special manifolding or pump
requirements, etc. The diversion of aqueous fluids occurs only
after the material enters the porous media, whether it is
naturally fractured carbonate/dolomitic rock or sandstone
matrix. It is theorized that the increased shear encountered
upon entering the rock matrix, coupled with polymer
adsorption, results in an apparent “viscosity” increase that may
be responsible for the pressure increases seen during the
treatment.14
Acid Diversion Testing
Laboratory testing indicated that the modified polymer could
effectively reduce permeability to water with little damage to
oil.12 Testing was then begun to determine whether the
polymer would be effective in diverting acid treatments.
Parallel core testing was used; polymer and acid were
bullheaded into a water-saturated core and an oil-saturated
core simultaneously. This testing has been previously
described in detail,13 and is summarized below.
Test 1 Series: Sandstone Cores Treated Separately
The initial experiments involved a relatively high-permeability
sandstone core (at residual oil saturation to represent a water-
bearing stratum) and a lower-permeability Berea sandstone
core (at residual water saturation to represent an oil-bearing
stratum). In these control tests, 13 pore volumes (PV) of 5%
HCl were pumped through each of these cores separately.
Each test resulted in more than a two-fold increase in
permeability, demonstrating that these cores were stimulated
by the acid treatment.14
Test 2 Series: Sandstone Cores Treated Simultaneously
The second test series again used a high-permeability core at
residual oil saturation and a lower-permeability core at
residual water saturation. However, in this case, the cores
were connected in parallel so that the treatment fluid could be
bullheaded into both cores simultaneously. The test
temperature was 175ºF. The treatment consisted of a 2,000-
ppm AP solution. The volume of treatment entering the water
core was 9 PV, and 0.8 PV entered the oil core before the 500-
psi pressure limitation was obtained. The fluid was flushed
from the lines and a spacer of 5% ammonium chloride was
pumped into the parallel core flow apparatus. All the spacer
was observed to enter the oil core (only 0.4 PV entered the
core before reaching the 500-psi pressure limit). After flushing
the spacer from the lines, a 5% HCl solution was pumped into
the parallel treatment apparatus.14
From a total 13 PV of acid, 11 PV entered the oil core and
2 PV entered the water core. The water core percent
permeability reduction was 96.5% while the oil core gave over
a two-fold increase in permeability (essentially the same as
observed in the control test with the oil core). Thus, the AP
not only effectively diverted the acid from the water core to
the oil core, it also very effectively decreased the permeability
of the water core while allowing stimulation of the oil core. 14
Test 3 Series: Berea Cores Treated Simultaneously
A third test series used two Berea cores, one at residual-oil
saturation and one at residual-water saturation. Again, the
cores were connected so that treatment fluids could be
bullheaded and the test temperature was 175ºF. A 2,000-ppm
AP solution was bullheaded into the cores. The water core
received 1 PV of the treatment while 0.8 PV entered the oil
core before the 500-psi pressure limitation. After flushing the
lines of the AP fluid, a spacer of 5% ammonium chloride
followed; 0.1 PV entered the water core and 0.2 PV entered
the oil core.
From a total 13 PV of 5% HCl, 10 PV entered the oil core
and 3 PV entered the water core. The water core percent
permeability reduction was 56% while the oil core again
showed an increase in permeability. 14
Test 4 Series: Carbonate Cores Treated Simultaneously
Previous testing focused on sandstone lithology; the fourth test
series used two Bedford limestone (carbonate) cores, one at
residual-oil saturation and one at residual-water saturation.
Again, the cores were connected so that treatment fluids could
be bullheaded and the test temperature was 175ºF. In this test
series, a control test was run in which acid alone was
bullheaded into the two cores. In this test, 14 PV of 5% HCl
entered the water core and 6 PV entered the oil core. In the
next test a 2,000-ppm solution of AP was bullheaded into the
two cores. Subsequently, 0.2 PV entered the water core and
1.6 PV entered the oil core. On the 5% ammonium chloride
spacer, 0.5 PV entered the water core and 0.2 PV entered the
oil core.
From a total 13 PV of 5% HCl, 2 PV entered the water
core and 11 PV entered the oil core. The oil core had a large
wormhole, while the water core appeared completely intact. 14
Test Results
These tests illustrate that the AP is capable of providing
diversion from a water-saturated core to an oil-saturated core,
SPE 107584
and is also capable of providing significant permeability
reduction to the water-saturated core.14
Test series 1–4, using the dual-core setup, were the basis
for establishing the capability of the AP to provide acid
diversion. As mentioned, the treatment stage with the polymer
ended when the differential pressure reached 500 psi. This
pressure buildup is one reason that the AP was recognized as a
potential acid diverter. A single-core test was used in an
attempt to determine the upper temperature limit of the
polymer for diversion applications. In this test, a core was
treated with 3,000 ppm polymer at 350°F. The pressure
reached 500 psi after pumping 9 PV of polymer, which is
typical of the volume pumped for all tests in this particular
rock. The initial permeability reduction was 99%. It was not
determined how long the polymer would remain stable and
hold this level of permeability reduction, but it does appear
that acid diversion could be obtained up to at least 350°F.14
This last assumption is now demonstrated with the results
shown in this paper.
Fig. 1—Oil and water Bedford limestone cores after APT
preflush/acid diversion test in parallel core flow test.
Reservoir Description of the Application Area
One of the most important of Mexico’s offshore projects is the
CLM (marine light crude) area. This project is a development
of seven fields in two distinctive phases: early production and
integral development.18
Fields A and B have been undergoing development for the
past two years and are located in the continental platform of
the Gulf of Mexico along the coast of the state of Tabasco,
approximately 80 km northwest of the Dos Bocas marine
terminal (Fig. 2). This field is in an anticlinal structure of
direction NE-SW, limited in its flank by a 10º to 12º inverse
fault that runs parallel to the axis of the structure. Toward the
NW, its closing is by an 8° dip of the structure, whereas
toward the SW, it is limited by an inverse fault that cuts its
main axis perpendicularly. Geologically, the field is located in
the denominated Campeche Bay basin. It consists of two
reservoirs that have important differences in terms of their
petrophysical characteristics and fluids. For the Cretaceus
formation, the rock trap is made up of carbonates and the trap
is of fundamentally structural character closed by the presence
3
of inverse faults and lateral displacement. The produced oil
has a density of 30°API.
For the Upper Jurassic reservioir, the dominant rocks are
dolomites in the base and limestones toward the central top.
As in the Mid-Cretaceus, the trap is combined by the influence
of sedimentological variation as much vertical as horizontal.
The oil has a density of 41° API. The wells in this study are
located on this reservoir.
Fig. 2— Location of the fields in the CLM area.
Field C was discovered in 1982 with drilling on the Brecha
Paleocene (BTP-KS), Middle Cretaceus (KM) and Lower
Cretaceus (KI) formations; it is a light oil producer of 32°
API. The geological structure of Field C is defined by a trap of
anticlinal type with direction NE-SW associated with an
aquifer considered to be 13,267 ft deep. A fundamental
characteristic of the field is the presence of a saline intrusion
that has the same direction of the structure and divides the
field into two blocks: eastern and western. Hydrocarbons of
the field are in carbonated formations in the column defined
between the Lower Paleocene and Lower Cretaceus, the latter
being of greater importance and denominated by a breach of
the Upper Paleocene-Cretaceus. Porosities fluctuate between
9% and 15%. In production terms, it is the main field of the
APC complex, nevertheless the advance of water-oil contact
has taken place mainly on the eastern side of the field.
Acid-Stimulation Challenges
Most of the wells located in Fields A, B, and C are producing
in low-permeability formations ranging from 5 to 30 mD.
Bottomhole static temperatures (BHST) in these wells are
often above 300ºF. These high temperatures limit acid
reactivity and penetration into the formation. Traditional acid-
stimulation jobs in this area are solvent/HCl/organic blends
designed to overcome sludge precipitation and high BHST. To
distribute acid along the producing intervals, viscocified acids
are often used as diverter systems with some success;
however, the high reservoir pressures of these fields limits
pumping rates. Lately, an acid-fracturing campaign has begun
in some of the fields in the CLM project. This campaign has
reported outstanding results, although several of the perforated
intervals in these wells are close to the oil-water contact,
4 SPE 107584

which limits the stimulation operations to matrix acid
treatments. Some additional work not yet published has
demonstrated that the AP can function as a fluid-loss control
agent.
Job Results
As mentioned, over 30 wells have been acidized using the AP
diversion system in offshore Mexico.14 Most of these wells
have permeabilties ranging from 100 to 1,000 mD. Although
the AP is a solids-free diverter, some concern existed when
applying this system about these low permeabilties because of
the way the AP attaches to the rock, which could cause a
reduced oil flow path and flow rate after stimulation. Results
from four jobs in low-permeability areas presented in this
paper have shown that the AP can be applied with success in
these situations. Table 1 shows results obtained from these
jobs, as well as, some results from the same well stimulated
using traditional methods, presented for comparison. Oil and
water production numbers shown are approximate values just
prior to and after acid stimulation.
antecedent the results obtained in other fields of the area in
which good production results were obtained even in
conditions where water cut was present.14 A combination of
solvent/acid was used to stimulate the well and in this case,
the AP was added as a diverter. The obtained production after
treating was of 9,700 BOPD with a drawdown pressure of
only 213 psi (Figs. 4 and 5). A new well test was performed
just after stimulation and showed that damage had been
removed to a skin value of 0.09. Using data available from the
well tests performed in both cases (post-stimulation
scenarios), an inflow performance curve (IPR) was adjusted to
visualize the benefit and better response of the acid
stimulation using the AP diverter against the previous
stimulation perfomed without the diverter (Fig. 6). The
increased production shown in Fig. 6 clearly shows the benefit
of the stimulation treatment applied with the AP. Another
benefit observed in the well after treatment was reduced water
cut, which decreased to 1.0% and stayed at that level
throughout the following months. Before stimulation, water
cut had been reported as 14.0%.

Field Case 1
Well A1 is located in Field A; it was completed in March
2005 in the Upper Jurassic formation, reaching a total depth of
18,822 ft with a final deviation of 22.5º. The BHST was 302ºF
and porosity was between 9 and 10%. The well was perforated
in the interval 18,602–18,700 ft, and current reservoir pressure
is around 9,100 psi. Just after its completion, the well was
evaluated using four different choke sizes, having reached a
production of 3,408 BOPD with a choke size of 1/2-in.. Based
on this information, the well was acid-stimulated to increase
its production, but the increase was minimal and the skin
factor in the formation was evident and verified by a well test
performed after cleaning, showing a skin factor of 22 (Fig 3).

Fig. 4—Pressure and derivative response of Well A1 after the

second acid-stimulation treatment with the AP diverter.

Fig. 3—Pressure and derivated response of Well A1 after the first

acid-stimulation.

Almost a year later, Well A1 was again given an acid-

stimulation treatment to obtain better productivity. Fig. 5—Production profile from Well A1.
Nevertheless, in February 2006, water cut appeared with
values of 7.0%, increasing gradually to values of 14.0% in
August 2006. These combined factors led to consideration of
using the RPM technology as a diverting system, having as an
SPE 107584
Fig. 6—Pre- and post-stimulation IPR curves for Well A1.
Field Case 2
Well A2 is also located in Field A. This well had been drilled
to a depth of 19,028 ft; the perforated interval was located
between 18,159 and 18,225 ft, with an average porosity of
11.0%. The BHST was 320ºF and the formation permeability
oscillated around 30 mD. This well was completed in
February 2004 with an original reservoir pressure of 11,300
psi. A production test performed in this well showed a
production of 8,575 BOPD. An acid-stimulation treatment was
performed using a traditional treatment based on a
solvent/acid blend along with viscosified acid as a diverter;
nevertheless the obtained production results showed no
increase in production. The well was put on production until
August 2006, when again it required an acid-stimulation
treatment because oil production had dropped slightly. Due to
the good results obtained in Well A1, it was decided to include
an RPM in the treatment to act as a diverter system during the
acid stimulation.
The results of the production rates before and after the
stimulation are shown in table 1, in order to evaluate the new
conditions of flow in the well, its IPR curve was adjusted
taking like reference the results from table 1. The increase of
production was of around 600 bopd and a drawdown pressure
of only 400 psi in the formation was obtained (Fig. 7).
Fig. 7—Pre- and post-stimulation IPR curves for Well A2.
Field Case 3
5
Well B2 is located in Field B. This well was drilled and put on
production in August 2006; the total depth reached was 20,111
ft with a deviation of 20°. The BHST was 323ºF with an
average porosity of 9–10%. The permeability of the formation
oscillated around 2–3 mD, and the producing interval was
located between 19,816 and 19,855 ft. Immediatly after its
completion, the well was evaluated with a production test
reporting oil production at close to 5,986 BOPD with a choke
size of 3/4-in.; water cut was 1.0%. Making use of the data
gathered in the production test, the inflow performance (IPR)
curve was built showing that well productivity behavior
matched with a skin factor of approximately +4. The well was
then stimulated using the AP as a diverting agent and another
production test was made on surface to evaluate the new flow
conditions of the well, which are shown in Table 1. With this
information, the new IPR curve was built, showing the
benefits gained for the acid stimulation; the oil rate increased
from 7,166 to 10,067 BOPD, whereas the drawdown pressure
decreased from 3,991 to 3,460 psi using a choke size of 1-in.
This increase in production reflects the success of the
stimulation for improving the flow conditions in the well.
As a comparison, results from an offset well (B1) will be
presented. The B1 well is also located in Field B and was
drilled to a depth of 19,685 ft. It was completed in the interval
18,405–18,471 ft in the Upper Jurassic formation in August
2005. The well was stimulated and a pressure test showed
3,201 BOPD to be the obtained benefit. This well has a
temperature of 335ºF and an average porosity of 10%;
according to well tests, permeability of the formation was
along the order of 1–2 mD. The initial pressure of the
reservoir was almost 10,383 psi, which often forced the use of
pumping up to 8,000 during the acid-stimulation treatments. A
year after the well was completed, it was chosen for an acid-
stimulation treatment and afterwards, oil production reached
4,200 BOPD with a choke size of 1-in (Fig. 8). It was treated
with the traditional solvent/acid blend but using gelled acid as
a diverter. The construction of the IPR curves before and after
the stimulation treatment shows a clear benefit in production
gained. However, drawdown pressure in the formation was
still of high magnitude, leaving this well a possible candidate
for greater potential, just like Well A2 (see Table 1).
Fig. 8—Pre- and post-stimulation IPR curves for Well B1.
6 SPE 107584

Table 1—Production Re s ults from Acid-Stim ulation Tre atm e nts

Prod.
Te m p., Re s e rvoir Initial Wate r Final Oil, Final Wate r
We ll Pe rm e ability Initial Oil, BOPD Incre m e ntal,
°F Pre s s ure Cut, % BOPD Cut, %
%
Before Stimulation After Stimulation
(W ithout AP Diverter) (W ithout AP Diverter)
A1 302 10.3 10131 3,425 0 3,153 0 -7.9
A2 320 30 10522 1,112 0 1,467 0 31.9
B1 335 2 9885 3,506 0 4,400 4 25.5
C1 275 26 3231 1,500 0 3,527 0 135.1
Before Stimulation After Stimulation
(W ith AP Diverter) (W ith AP Diverter)
A1 302 10.3 9161 3,461 14 9,700 1 180.3
A2 320 30 9316 4,500 1 5,660 1 25.8
B1 323 2 11876 7,166 0 10,067 0 40.5
C1 275 26 3231 2,599 0 5,192 0 99.8

Field Case 4
The C1 well is located in the Field C. This well was drilled to
a depth of 13,123 ft and was perforated in the interval 12,942–
13,057 ft. It has an average porosity of 8.0%, and the BHST
was 275ºF. The permeability of the formation oscillates
around 26 mD. The well was stimulated in September 2005,
obtaining an acceptable increase of oil production from 1,500
to 3,500 BOPD. Nevertheless, a well test revealed a remaining
skin factor of +5.0 even after the stimulation (Fig. 9). The well
was put on production for almost a year when it was decided
to acid stimulate it again because production had decreased to
values of around 2,500 BOPD. A production analysis showed
that the well behavior adjusted to a skin factor of close to +18.
For that reason, an acid-stimulation treatment was scheduled
to restore production to its initial levels before the decrease. In
this treatment, the stimulation included the AP as a diverting
agent. Following the acid stimulation, oil producion reached
5,192 BOPD with a choke size of 2-in. Fig. 9—Pressure/derivated response for Well C1 after the first
acid stimulation.
As in the previous cases, production data was gathered to
build the new IPR curve (Fig. 10) and ascertain how the skin
factor affected production (Fig. 11). The skin factor better
matched the surface pressure, and production was -3. The
results of the oil rates before and after the stimulation are
shown in Table 1. Fig. 12 shows production comparisons for
acid-stimulation treatments with and without the AP diverter
for all the wells presented.

Conclusions
• Laboratory tests show that the AP diverter can divert
acid from predominantly water-saturated zones to
predominantly oil-saturated zones in both sandstone
and carbonate lithology.
• In sandstone and carbonate, the AP diverter can provide
acid diversion and permanent water-permeability
reduction.
• Results from Fields A, B, and C show that the use of
the AP diverter resulted in a better production response Fig. 10—Pre- and post-stimulation IPR curves for Well C1.
compared to previous acid-stimulation treatments in
which different diverters were used.
SPE 107584 7

Nomenclature
BHST = bottomhole static temperature
BOPD = barrels of oil per day
cp = centipoises
in. = inches
mD = milidarcies
min = minutes
mL = milliliters
psi = pounds per square inch
ppm = parts per million

Acknowledgements
The authors would like to thank Petroleos Mexicanos and
Halliburton management for their support and permission to
publish this paper. Thanks also to Larry Eoff and Dwyann
Dalrymple for their advice and support.
Fig 11—Production profile from Well C1.

Fig. 12—Production comparison of acid stimulation treatments with AP diverter against wells without AP.
8 SPE 107584
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