SPE 121143

Successful Field Application of a High-Temperature Conformance Polymer

in Mexico
Modesto Mercado and Juan Carlos Acuna, PEMEX, and Julio Vasquez, Carlos Caballero, and Eduardo Soriano,
Halliburton

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE European Formation Damage Conference held in Scheveningen, The Netherlands, 27–29 May 2009.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Conformance-polymer systems have been successfully applied for many years to control undesired water production from
hydrocarbon wells. However, currently available polymers present a number of limitations for high-temperature wells
(>250°F) in terms of providing longer gelation times and acceptable thermal stability. This paper presents the successful field
implementation of an organically crosslinked polymer (OCP) for high-temperature applications in southern Mexico.
The OCP system is based on a copolymer of acrylamide and t-butyl acrylate (PAtBA) crosslinked with
polyethyleneamine (PEI). To date, more than 450 jobs have been performed with the OCP system around the world to
address conformance problems, such as water coning/cresting, high-permeability streaks, gravel pack isolation, fracture
shutoff, and/or casing-leak repair. Originally, the OCP system had a limited working temperature range from 100° to 250°F.
The upper placement temperature of the system was ~250°F because, above this temperature, pumping times were too short.
A recently developed carbonate retarder allows reasonable placement times up to 350°F, without the need for cooling down
the formation to obtain enough pumping time. The retarder is not detrimental to the thermal stability of the system.
An overview of case histories that used OCP in southern Mexico is presented in this paper. In addition, the development
results of the high-temperature conformance polymer are discussed in terms of (1) gelation-time measurement and (2)
effectiveness to limit permeability to water and thermal stability in sandpack flow tests at elevated temperatures. To date,
more than 70 jobs have been successfully performed worldwide with the OCP at temperatures higher than 250°F.

Introduction
Excessive water production from hydrocarbon reservoirs is one of the most serious problems in the oil industry. Water cut
greatly affects the economic life of producing wells. Unwanted water production is estimated to cost the petroleum industry
about $45 billion each year, although accurate records of water production are difficult to obtain (Conformance Technology
Manual 1996; Curtice and Dalrymple 2004). The southern region of Mexico presents a major challenge with water
management as well. Water production results in extra disposal costs, scale buildup, reduced oil production, and eventually
well abandonment (with associated workover costs). Consequently, producing zones are often abandoned in an attempt to
avoid excessive water production, even when intervals still retain large volumes of recoverable hydrocarbons.
Although natural fractures have a positive effect on oil flow, they also negatively impact water and/or gas flow caused by
coning effects or high-permeability streaks between the producing hydrocarbon zone and intervals above and/or below. If
these zones contain high mobile-water saturation, they soon will impact the productivity of the hydrocarbon zone. Early
water breakthrough caused by edge-water flowing through faults or natural fractures is another common problem in this
region. In addition, many of these formations with high-water-management problems produce from intervals with bottomhole
temperatures higher than 250°F, hence the need for a high-temperature, porosity-fill sealant in this temperature range.
Remediation techniques for controlling water production, generally referred to as conformance control, include the use of
polymer systems to reduce or plug permeability in the water-producing intervals. This paper discusses water control in high-
temperature environments (>250°F) for treating hydrocarbon-producing wells to reduce water production for applications in
which water and hydrocarbon zones are clearly separated. The principle of operation of this technique is to pump the polymer
system into the formation around the wellbore and allow it to propagate through the rock matrix. In-situ gelation takes place,
plugging pore spaces and channels, thus, limiting undesired water flow (Dalrymple et al. 1994). A variety of techniques for
controlling water production have been attempted by the oil industry. Earlier attempts to reduce water production included
2 SPE 121143

mechanical isolation, squeeze cementing, solid-slurry (clay) injection, and oil/water emulsion. More successful results have
been obtained with in-situ polymerized systems, crosslinked polymeric solutions, and silicate-based gels (Prada et al. 2000).
Polymer-gel systems have emerged during the last decade as one of the most effective tools for controlling water
production. One of the most widely used polymer systems employs polyacrylamides (PAms) or acrylamide co-polymer and
chromium [Cr(III)] as a crosslinker (Sydansk 1990). Cr(III) has been extensively used because of its high success rate and
relatively low cost. However, the short gelation times of this system at elevated temperatures limit its application to low- to
moderate-temperature reservoirs (Bartosek and Lockhard 1994). Another polymer system widely used is a water-based gel
based on phenol/formaldehyde crosslinker for homo-, co-, and ter-polymer systems containing acrylamide. The loss of
phenol by partitioning when it comes into contact with crude oil has been identified as an important issue for that polymer
system (Albonico et al. 1995). The toxicity issues associated with formaldehyde and phenol have been addressed by other
researchers (Moradi-Araghi 1994).
Systems-based on PEI as a crosslinker and a base copolymer of acrylamide and PAtBA have been reported to propagate
deep into the matrix to provide excellent thermal stability. Although this polymer system has been successfully implemented
in field operations, some features need improvement for high-temperature reservoirs (i.e. gel times are too short at
temperatures higher than 250°F) (Reddy et al. 2002; Vasquez et al. 2003). The challenge for high-temperature applications is
mainly the capability to provide longer gelation times and acceptable thermal stability. This paper presents the results from a
laboratory evaluation that evolved to address these high-temperature issues, and it is a continuation of the investigation
published in SPE 93156 (Vasquez et al. 2005).

Description of the Organically Crosslinked Polymer (OCP) System

The base polymer is a copolymer of acrylamide and PAtBA. The organic crosslinker is a low-toxicity material based on PEI.
The amine groups on PEI react with the amide (and probably with the ester groups) to form an amide linkage. Because of the
presence of multiple amine groups on the PEI and ester/amide groups on the PAtBA, this results in a crosslinked, three-
dimensional gel structure. The short gel times are thought to be caused by increased reaction rate of the PEI amine groups
with the polymer ester/amide groups. To make this polymer system work at higher temperatures in the past, a preflush phase
would be required to cool down the zone to ~250°F so that the polymer system could be placed before gelling. A recently
developed carbonate retarder has been added to the system to delay its crosslinking time. The general crosslinking
mechanism for this system is illustrated in Fig. 1.

Fig. 1—OCP system general crosslinking mechanism (X = O, N; R = C(CH3)3, C(CH3)2, NH2, CH2SO3H, N(CH3)2).

The scope of this laboratory evaluation was divided into two major phases: (1) gelation time measurement as a function of
temperature and (2) the ability of the OCP system to reduce effective permeability to water and provide thermal stability at
350°F.

Gelation-Time Evaluation of the OCP System

Gelation time is one of the most important characteristics of a polymer system because it defines the pumping time available
to safely place the system into the matrix of the rock. Gelation time corresponds to the inflection point of the viscosity-versus
time curve. Fig. 2 illustrates a typical plot of viscosity-versus-time for the OCP system (gelation time is approximately 13
hours at 300°F for this particular test). Gelation time needed for a particular application will be dictated by reservoir
conditions, such as reservoir depth, length of the interval to be treated, bottomhole temperature, injection rate, and shut-in
time program, among others.
SPE 121143 3

Fig. 2—Typical gelation-time curve using a Brookfield high-pressure PVS viscometer (gelation time is approximately 13 hours at
300°F).

Without the addition of the carbonate retarder, gelation times for the OCP system were short at temperatures higher than
250°F (less than 2 hours). Fig. 3 shows the gelation-time curves for the OCP system from 250°F to 350°F, varying the
retarder concentration. Other parameters, such as crosslinking concentration, mixing brines, and pH were investigated but
results were not included in this publication. The OCP system has been previously tested to be resistant to acid, CO2, and
H2S. For high temperatures, the use of high-PAtBA concentrations (i.e. 7% active) is recommended to obtain a more
thermally stable gel. A good gel quality was observed with the addition of the retarder. The addition of this retarder to the
OCP system expands the temperature range of applicability of the current commercial system, allowing the elimination of the
cooling preflush stage and simplifying the job design and execution.

Fig. 3—Gelation-time data with the recently introduced water-soluble carbonate retarder from 250°F to 350°F (7% active PAtBA,
0.66% PEI, in 2% KCl, varying the retarder concentration at various temperatures).
4 SPE 121143

Evaluation of the OCP System’s Ability to Reduce Effective Permeability to Water and Provide Thermal Stability
Sandpack flow tests were conducted to evaluate the effectiveness of the OCP system to limit permeability to water at 350°F.
Fig. 4 illustrates the experimental equipment used to simulate high-temperature and high-pressure reservoir conditions.
Before water and kerosene were injected into the sandpacks, the fluids were filtered through a 2.0-μm filter to remove any
particulate matter from the fluids. After flowing through a check-valve, water and kerosene flowed through a coiled-tubing
heating bath to reach test temperature. After flowing through the sandpacks, the fluid temperature was decreased by forcing
the exiting fluids through a cooling coil. Finally, fluids exited the system through a backpressure regulator, holding a system
pressure of approximately 200 psi. Testing temperature was 350°F. Sand was packed in 21.5-cm long, 1.5-cm inside diameter
Monel tubes. Sand formulation consisted of a mixture of sand (70 to 325-US Mesh) and bentonite.

Fig. 4—Experimental setup for dynamic core and sandpack flow tests.

Sandpacks were saturated with water at testing temperature. Water was flowed until a stable pressure drop was recorded,
at which point, the absolute permeability of the sandpack was calculated. Next, 150 mL of kerosene was injected into the
sandpack at testing temperature. Finally, water was injected again to reach residual-oil-saturation conditions until stable flow.
At this condition, the effective permeability to water at residual-oil saturation kwro was calculated. The absolute water
permeability, effective permeability to water at residual-oil-saturation kwro, and the treated effective permeability within the
sandpack were calculated using Darcy’s flow equation:

qμ L
K= .……………………………………………….………..…..……..….(1)
A ΔP
where K is the permeability in Darcy (0.986923 μm2), q is the flow rate in cm3/min, μ is viscosity at temperature in cP, A is
the cross-sectional area of the sandpack in cm2, L is the length of the sandpack in cm, and ΔP is the differential pressure
along the sandpack in atm.
SPE 121143 5

At this point, the sandpack was considered ready to be treated. The treatment (consisting of 10 pore volumes (PV) of the
OCP system) was injected into the sandpack. At the end of the treatment placement, the sandpack was shut in overnight to
allow for gelation. Table 1 shows the results of this flow test at 350°F. The percent permeability reduction (PPR) is given by:
⎛ Kf ⎞
PPR = 100 ⎜⎜1 − ⎟⎟ ………………………………….…………….……...…..(2)
⎝ K i ⎠
where the subscript i indicates the initial permeability at residual-oil saturation conditions, and the subscript f indicates the
final permeability after the sandpack was treated. In addition, core tests in sandstone and carbonate cores were performed
(results are not included in this publication). The second objective of this test was to evaluate the long-term sealant properties
of the OCP system at 350°F.
Table 1 shows a detailed description of the OCP-system formulation used for this flow test. The effective permeability to
water was significantly decreased after the injection of the OCP system into the sandpack. In addition, Fig. 5 shows the
percent permeability reduction after aging this test at 350°F. The OCP system was thermally stable after 30 days of exposure
to 350°F, showing 100% permeability reduction (no flow).

Table 1—Summary of Sandpack Flow Test with the OCP System at 350°F
(7% Active PAtBA, 0.66% PEI, 6% Retarder, in 2% KCl)
Water absolute permeability, mD 1692.4
Water effective permeability at Sor, mD 1669.2
a
Water effective permeability after treatment, mD 0
Permeability reduction, % 100
a
Sandpack treated with 10 PV

Fig. 5—Summary of aging test with the OCP system after 30 days of exposure at 350°F (7% active PAtBA, 0.66% PEI, 6% retarder, in
2% KCl).

Case Histories in Southern Mexico

The field in reference is an asymmetric, anticlinal geologic structure with NW-SE direction affected by normal and inverse
faulting with the presence of saline intrusions to the north and the south of the structure. The gross thicknesses of the rocks
that lodge the deposit vary from 417.9 to 1,594.9 m (1,371 to 5,233 ft), whereas, the net thickness varies from 331.9 to 1,341
m (1,089 to 4,400 ft).
The extension of the producing area is 28.26 square miles, including the Lower Cretaceous formation and the Upper
Jurassic Kimmeridgiano. These are naturally fractured deposits formed by limestone and dolomites with permeability that
varies from 10 to 120 mD, and average gross thicknesses between 1,016 to 1,200 m (3,280 and 3,937 ft). The reservoir is
6 SPE 121143

located at depths of 4,599.2 to 6,400.5 m (15,090 to 21,000 ft). The reservoir holds a volatile oil deposit of 38° API, with an
initial pressure of 10,056 psi, and a bubble pressure of 3,726 psi. Currently, the reservoir is under depleted conditions with an
actual reservoir pressure of 3,130 psi and an average bottomhole temperature of 307°F. The recovery mechanism is a water
drive, and the depth of the original oil-water contact was located at 21,077 ft. The current oil-water contact varies along the
field and is influenced by the extensive net of natural fractures and faults.
The case histories discussed in this paper are located in southern Mexico. (Fig. 6).

Fig. 6—Geographic area.

Producing zones lie within carbonate reservoirs drilled at depths that, in some cases, reach 6,004 m (19,700 ft) TVD. The
producing formations vary in lengths from 200 to 350 ft but, in some cases, they exceed this thickness range. The main
mechanisms of production in this area are natural fractures located along the entire producing interval. Matrix porosities vary
from 2–8%. These reservoirs are basically depleted and classified as mature. Most of the wells located in these fields require
gas lifting to sustain oil production. Bottomhole temperatures of these reservoirs oscillate around 300°F. They are mostly
water-drive reservoirs in which the water-oil contact is not well known.
As previously mentioned, although natural fractures have a positive effect on oil flow, they also negatively impact water
and/or gas flow caused by coning effects or high-permeability streaks between the producing hydrocarbon zone and intervals
above and/or below. If these zones contain high mobile-water saturation, they soon will impact the productivity of the
hydrocarbon zone. Early water breakthrough caused by edge-water flowing through faults, or natural fractures, is another
common problem in this southern region. This demonstrates one of the reasons fluid flow is difficult to characterize in a
uniform pattern in these reservoirs. Throughout the past four years, many OCP treatments have been successfully performed
in this region of Mexico in formations with BHT higher than 250°F, with the aid of preflushes to cool down the formation
and avoid premature gelation problems. The development of this carbonate retarder allows for an easier pumping schedule as
well as the treatment of several candidates at higher temperatures (up to 350°F) for conformance control.
Four case histories are presented in this paper as illustrated in Table 2. Two of the three treatments were bullheaded into
the wellbore and one was performed with the aid of coiled tubing to target a particular zone. A typical operation procedure
for the two rigless jobs (bullhead treatment) is shown below:
• The well is tested for admission and the treatment volume is redefined, if needed.
• Casing integrity is tested by pressurizing it up to 500 psig.
• A spacer (previously tested for compatibility with the OCP system) is bullheaded at matrix rates.
• The OCP system is pumped at matrix rates (and at maximum possible pumping rate).
• A small tail-in of foamed-cement slurry is pumped at the maximum possible rate.
• Displacement with a linear gel spacer is initiated at the maximum possible pumping rate.
• Displacement is completed to the top of the perforations with fresh or treated water.
• The well is then shut in for 24 hours.
SPE 121143 7

Table 2— Wells Treated with OCP System

BHST, Placement
Well No. Interval, o Lithology
F Technique
1 5,201.7–5,527.6 m (17,067–18,136 ft) 300 Carbonate CT
2 5,310–5,359.6 m (17,421–17,585 ft) 300 Carbonate Bullheading
3 5,654.7–5,672.7 m (18,553–18,612 ft) 306 Carbonate Bullheading
4 5,457.2–5706.2 m (17,905–18,722 ft) 305 Carbonate CT

Well 1 Case History

Well 1 is a vertical, cased-hole well drilled at 5,518 m (18,100 ft) and completed in an openhole section of 326 m (1,070 ft)
of carbonate formation (Fig. 7). Well 1 was initially acid-stimulated to improve oil production; however, a water cut of
almost 90% was observed after this stimulation treatment. The customer then decided to attempt to decrease water production
by pumping the OCP system followed by a small tail-in of foamed cement. This operation was carried out with CT in three
stages, alternating the OCP system and the foamed cement. The three OCP/foamed-cement stages performed focused on
sealing-off a net of natural fractures present at the bottom of the openhole section. After the third stage was complete, the
well was shut in overnight to allow the systems to fully crosslink. Following the treatment, the remaining exposed openhole
section was acid-stimulated and the well was put back in production. Fig. 8 illustrates the results of the treatment that
decreased the water cut from 90.0% to 0.2%, even two years after the OCP treatment was performed.

Fig. 7—Well 1 schematic and openhole log interpretation highlighting the zone treated with the OCP system.
8 SPE 121143

Fig. 8—Well 1 water cut production history.

Well 2 Case History

Well 2 is a vertical, cased-hole well perforated at 5,669 m (18,600 ft) (Fig. 9 shows wellbore schematic). This well produced
oil for a period of almost ten years at low rates of water production until it slowly started increasing up to 97% water cut. The
interval was isolated with a mechanical plug and then a new interval was perforated at 5,303 m(17,400 ft). This new interval
again started producing water and then the customer considered the option of an OCP treatment to shut off the water. The
OCP system, along with a small tail-in of foamed cement, was bullheaded into the formation to seal off this interval. The well
was shut in overnight. The interval was reperforated, but this time only the top 37.8 m (124 ft) of the original 59.7 m (196 ft)
of perforations were reopened and followed with an acid-stimulation job. This treatment resulted water-free oil production.
As Fig. 10 illustrates, Well 2 was producing at 5% water cut after two years.
SPE 121143 9

Fig. 9—Well 2 wellbore schematic showing the zone treated with the OCP system.
10 SPE 121143

Fig. 10— Well 2 water cut production history.

Well 3 Case History
Well 3 is also a vertical, cased-hole well perforated at the interval from 5,585–5,595 m (18,319–18,351 ft) (Fig. 11). This
interval eventually reached water cut values of 3–45%. Similar to the previous two case histories, the OCP system was
pumped followed with a small tail-in of foamed cement. The treatment was bullheaded and then shut in overnight. The
customer decided to perforate a few feet up the isolated interval at 5,529.7 m (18,143 ft) in the same carbonate formation
followed by an acid stimulation treatment. Water cut has been ~4% even two years after the OCP treatment was performed
and after two acid stimulations were performed during this period (Fig. 12).

Fig. 11—Well 3 wellbore diagram and openhole interpretation.

SPE 121143 11

Fig. 12—Well 3 water cut production history.

Well 4 Case History

Well 4 is a deviated well drilled at a total measured depth of 6,000 m (19,680 ft) (Fig. 13). This well was completed with an
exposed openhole interval of 250 m (818 ft). This openhole section was acid-stimulated, inducing water production to an
average of 60%. To decrease water production, the OCP system was pumped with the aid of CT followed with a small tail-in
of foamed cement. After the treatment, the water cut dropped to 2–10% and remained stable for a period of 5 months. After 5
months of production, customer decided to acid-stimulate this interval for the second time to improve oil production,
inducing an increase of water production to 30% water cut. A second OCP treatment was performed with the aid of CT,
yielding an immediate water cut reduction to 2%. This percentage has remained stable for two years, even when two
additional acid treatments have been performed, causing some peaks of water production reaching 30%, which then became
stable again at about 2–5% (Fig 14).

Fig. 13—Well 4 wellbore diagram and openhole interpretation.

12 SPE 121143

Fig. 14—Well 4 water cut production history.

A brief summary of the water-cut behavior of the four cases is presented in Table 3, tracking the water cut up to one year
after the OCP treatment was performed.

Table 3—Case Histories with the OCP System

Water cut, %
Well No. Before 30 Days after 90 Days after 120 Days after 360 Days after
Treatment Treatment Treatment Treatment Treatment
1 90.0 0.1 0.4 0.3 0.2
2 97.0 0.5 0.5 0.5 5.0
3 44.0 7.0 4.0 4.0 4.2
4 60.0 30.0 6.0 2.0 2.0–5.0

Conclusions
Conclusions of this work are presented below.
• The development of the new carbonate retarder extends the temperature range of application of the OCP system up
to 350°F. Reasonable gelation times can be achieved up to 350°F, without the need of cooling down the formation to
obtain enough pumping time. The retarder is not detrimental to the thermal stability of the system.
• Based on the laboratory evaluation, the OCP system provides excellent permeability reduction and good thermal
stability at 350°F. No injectivity problems were observed during the flow tests.
• The OCP system has been successfully implemented in the field for high-temperature applications. To date, more
than 70 jobs have been performed with the recently developed retarder with temperatures higher than 250°F.
• The OCP system has been previously tested to be resistant to acid, CO2, and H2S.
• The OCP system is able to address conformance problems, such as water coning/cresting, high-permeability streaks,
gravel-pack isolation, fracture shutoff, and casing leak repair. The OCP system has proven to be successful (more
than 450 jobs) in various regions throughout the world for sandstone and carbonate formations.

Nomenclature
A Cross-sectional area, cm2
Atm Atmosphere
BHT Bottomhole temperature
d Diameter, cm
K Permeability, mD
Kf Final permeability, mD
Ki Initial permeability, mD
kwro Effective permeability to water at residual oil saturation, mD
L Core length, cm
PAtBA Polyacrylamide t-butyl acrylate
PEI Polyethylenaimine
PPR Percent permeability reduction
SPE 121143 13

Q Flow rate, mL/min

t Time, days
T Temperature, oF
TVD True vertical depth
ΔP Pressure drop along the core, psi and atm.
Δ Change, drop
μ Viscosity, cP
f Final
i Initial
o Oil
w Water

Acknowledgements
The authors thank PEMEX and Halliburton for support and permission to publish this paper.

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