SPE 127981

Successful Water-Shutoff Case Histories in a Naturally Fractured Carbonate

Reservoir in Offshore Mexico Using an Organically Crosslinked Polymer
System With a Modified Tail-In
R. Hernandez, Pemex; J. Vasquez, V. Cancino, E. Soriano, Halliburton

Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the 2010 SPE International Symposium and Exhibition on Formation Damage Control held in Lafayette, Louisiana, USA, 10–12 February 2010.

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
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Abstract
This paper presents the laboratory development and successful field implementation of an organically crosslinked polymer
(OCP) system for water- and gas-shutoff applications. An overview of case histories in a naturally fractured carbonate
reservoir (with BHT >250°F) in offshore Mexico where the OCP was successfully applied to reduce water production is
presented. To control overdisplacement of the treatment, a modified tail-in combining the OCP system with inert particles was
used to provide leakoff control, resulting in a controlled placement of the sealant.
The OCP system is based on a copolymer of acrylamide and t-butyl acrylate (PAtBA) crosslinked with polyethyleneimine
(PEI). To date, more than 600 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. The development results of this OCP system are discussed regarding its activation time and its effectiveness to limit
permeability to water and provide thermal stability in sandpack flow tests at elevated temperatures. Lastly, the combination of
the OCP system with inert particulates to provide fluid-loss control is discussed.
The OCP system has been successfully applied to sandstone, carbonate, and shale formations in need of conformance
treatments. This system has been successfully tested to withstand a differential pressure of at least 2,500 psi and is resistant to
acid, CO2, and H2S environments. Because of the ability of the OCP system to withstand pressure, workover operations have
been successfully performed in previously treated wells including acid-stimulation, sand-control, and frac-packs treatments,
among others. An overview of case histories in which the OCP system was used in offshore Mexico is presented. This
advanced water-control technology has extended the well life and profitability of the treated wells. In the past, many of these
wells were abandoned because of the limited water-handling facilities.

Introduction
Excessive water production from hydrocarbon reservoirs is one of the most serious problems in the oil industry. 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. This paper discusses a chemical treatment in 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 (Prada et al. 2000).
The OCP system described in this paper has been widely used in the oil industry to address conformance problems, such as
water coning/cresting, high-permeability streaks, gravel-pack isolation, fracture shutoff, and/or casing-leak repair (Vasquez et
al. 2003; Vasquez et al. 2005).
2 SPE 127981

Description of the Water-Control System

Description of the Organically Crosslinked Polymer (OCP) System

The sealant system described in this paper uses a copolymer of acrylamide and t-butyl acrylate crosslinked with
polyethyleneimine (PEI). The general crosslinking mechanism for this system is illustrated in Fig. 1. This system has a
temperature range from 70 to 350°F (21 to 177°C). The sealant system components are easily diluted in the mixing brine. The
crosslinking process is activated by the temperature of the well. The crosslinking rate is dependent on temperature, salinity,
pH, and base polymer and crosslinker concentrations. The sealant system offers the following advantages:
• It is a low-viscosity fluid system (20 to 30 cP) that can be easily injected deep into the matrix of the formation
without undergoing hydrolysis and precipitation. It is well-known that chrome-based systems tend to hydrolyze and
precipitate, especially with increasing pH and temperature (Lockhart and Albonico 1992).
• It provides adequate pumping times in environments up to 350°F (177°C) to obtain adequate placement time before
the system undergoes the phase change from liquid to a three-dimensional gel structure. This transition time is
completely controllable and predictable with the crosslinker concentration for a given temperature. Fig. 2 illustrates a
typical plot of viscosity versus time for the OCP system. The inflection point of this plot corresponds to the gelation
time of the 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.
• It provides effective water-permeability and gas-permeability reduction and sufficient strength for resisting
drawdown pressure inside the wellbore and stopping water and gas flow. The system provides sufficient strength for
resisting differential pressures of at least 2,500 psi (based on laboratory data).
• Thermal stability has been tested up to 375°F (191°C).
• In addition, the OCP system is not sensitive to formation fluids, lithology, and/or heavy metals. Previous publications
summarize both laboratory data and a number of case histories for both water and gas shutoff (Eoff et al. 2006).

Fig. 1—OCP system general crosslinking mechanism (X = O, N; R = C(CH3)3, C(CH3)2, NH2, CH2SO3H, N(CH3)2).
SPE 127981 3

Fig. 2—Typical gelation-time curve using a Brookfield high-pressure PVS viscometer (gelation time is approximately 13 hours at
300°F).
Sandpack flow tests were conducted to evaluate the effectiveness of the OCP system to limit permeability to water at
350°F. 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 were flowed through a coiled-
tubing (CT) 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.
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.
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 the successful results of a sandpack flow test where the OCP system was evaluated; a detailed description
of the formulation used in the test is provided as well. The effective permeability to water was significantly decreased after the
injection of the OCP system into the sandpack. In addition, Fig. 3 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).
4 SPE 127981

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 1069.2
a
Water effective permeability after treatment, mD 0
Permeability reduction, % 100
a
Sandpack treated with 10 PV

Fig. 3—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).

Modified Organically Crosslinked Polymer (m-OCP) System

The m-OCP serves as tail-in for the main OCP treatment. The m-OCP combines the organically crosslinked porosity-fill
sealant with inert particulates to provide leakoff control, resulting in a shallow and controlled penetration to avoid
overdisplament of the main treatment and obtain a good seal in the near-wellbore region. After the m-OCP system screens out
at the formation face, the well is shut in to allow the base fluid to crosslink. The system can be easily washed out of the
wellbore compared to cement, which must be drilled out. Selective perforation of the oil zones re-establishes the desired
hydrocarbon production from the targeted interval.
In the original formulation of the m-OCP system, cement was considered as the particulate material (van Eijden et al.
2004). The idea was to have both a hard-setting material, such as cement, as well as the filtrate, that would gel and aid in
blocking fluid flow. A few jobs were performed with this combination, but it was later decided to replace cement with inert
particulates because (1) chemical interaction of the sealant system with cement would change the setting times of both systems
and (2) sealant/cement volume left in the wellbore would have to be drilled out (van Eijden et al. 2005). It was then decided to
investigate different inert particulates that would not change the activation time of the organically crosslinked porosity-fill
sealant and would allow easier wellbore cleanup. A variety of inert particulates were evaluated and provided excellent fluid-
loss control properties without changing the activation time of the sealant system. Some of the evaluated inert particulates are
silica flower, calcium carbonate, starch, and a water-swelling polymer (Abbasy et al. 2008), among others.
Currently, silica flour is the inert fluid-loss additive of choice for the OCP system. About 100 m-OCP jobs have been
performed with this system to date for water- and gas-shutoff applications, such as zonal isolation, casing-leak repair, sealing
of thief zones, and many other wellbore operations.
Fig. 4 illustrates that the addition of the silica flour to the sealant slightly changes the gel times of the system (neat-OCP
system versus filtrate for the m-OCP system). Therefore, the only design criteria for this system is to determine the gel time of
the sealant formulation, which is based on the temperature and amount of time needed to place and squeeze the treatment.
SPE 127981 5

Fig. 4—Gel times: neat-OCP system vs. filtrate from the m-OCP system.

The laboratory work performed to prove the ability to provide leakoff control and an adequate seal was conducted using
cores (3-in. length and 1-in. diameter) in Hassler sleeves. Representative data from this testing is shown in Table 2. The cell
was modified so that the OCP slurry could be spotted to the core face and pressure applied to allow filtrate leakoff. In these
tests, 500-psi differential pressure was applied for 30 minutes, followed by an overnight shut-in to allow filtrate gelation. The
following day, brine was pumped against the opposite core face.
The variables investigated were temperature, permeability, and percent silica flour (measured as % weight of the total
mixture). As shown, the amount of leakoff and the pressure required to initiate flow of the brine was independent of the
temperature or the core permeability. However, the percent silica flour influenced the amount of leakoff observed. The
formulations containing 50% silica flour had an average total leakoff of 13 mL. The formulations containing 35% silica flour
had an average leakoff of 63 mL. Therefore, 50% silica flour was chosen for field usage. Note that, in most of the tests, 1,000
psi or greater differential pressure was applied to the cores with no resulting flow of brine. In two cases, brine flow was seen at
differential pressures less than 1,000 psi, but the calculated permeability reduction was higher than 99%. In addition, this
system has been successfully tested to withstand a differential pressure of at least 2,500 psi.

Core Data
Silica Fluid Loss (mL of Filtrate at Given Time in Minutes) Pressure
Core Brine
Flour by Applied to
Temp, °F Permeability, 1
Weight , Spurt 1 2 5 10 30 Initiate
???
% Flow, psi
2
50 2.8 6.1 7.2 8.3 92 11.6 1,000
2
190 128 50 3.1 6.6 8.2 9.1 9.8 11.8 1,000
2
190 92 35 5.8 12.8 18.7 32.0 46.0 55.5 1,000
2
190 128 50 2.2 5.2 8.1 10.6 11.4 13.4 1,000
3
190 101 50 0.1 0.9 2.0 4.2 7.0 9.5 471
2
190 3,115 50 2.5 6.0 8.5 10.0 10.8 13.0 1,165
2
230 119 50 3.5 8.7 9.3 10.6 12.0 18.0 1,000
2
230 105 35 6.1 15.3 23.8 422 55.5 71.0 1,000
2
260 124 50 5.0 7.0 8.6 10.0 12.5 17.0 1,000
3
260 121 35 8.2 20.0 33.0 41.0 47.0 62.0 571
2
260 60 50 1.5 5.1 8.5 9.8 11.2 14.1 1,271
1
By weight of total mixture
2
No flow
3
Flow initiated at this pressure; permeability reduction was 99%

Case Histories in Southern Mexico

The Caan field is located on the continental shelf of the Gulf of Mexico, off the coast of Tabasco and Campeche,
approximately 82 miles from the Dos Bocas Marine Terminal in Paraíso, Tabasco and approximately 50 miles northeast from
Ciudad del Carmen, Campeche. This project includes four fields, which are offshore complex facilities and are strategic for
6 SPE 127981

managing the production at the Southwestern Marine region .The main reservoir rocks are dolomitic carbonated breccias from
the Upper Cretaceous-Lower Paleocene (K-T). They consist of 164 to 492 ft of coarse-grained carbonated breccias strongly
dolomitized and naturally fractured with secondary vuggy porosity due to diagenetic dissolution processes, having a porosity
range from 6 to 14% and permeability from 100 to 3,000 mD. Hydrocarbon production from these reservoirs has an oil gravity
of ~30 API.

To date, more than 600 jobs have been run with the OCP system to cover a wide variety of conformance problems for both
water and gas shutoff. The application of the OCP in Mexico has been amply documented in previous publications (Mercado
et al. 2005; Vasquez et al. 2005).A few case histories are described below related to the rising of the water-oil-contact (WOC)
in the Caan, field which becomes a major challenge in terms of excessive water production. The case histories discussed in this
paper used the m-OCP as a tail-in of the main treatment to avoid overdisplacment of the OCP system in the near-wellbore
region caused by the existence of fractures and the low formation pressure of these formations, as shown on the Fig. 5.

Fig. 5–Typical water shutoff-treatment in the Caan Field: (a) water-oil-contact (WOC) rising and reaching the perforated interval; (b)
injection of the OCP and m-OCP treatments to form a barrier inside the formation and prevent the WOC from rising; (c) reperforation a
few feet up in the same pay zone.

The simplest, most economical treatment placement method is the bullheading technique, in which the treatment is injected
through existing tubulars. This technique can be used effectively for entry into zones that will take 100% of fluids or for entry
into perforations where a permeability decrease is necessary. To design an effective placement procedure and responsive
treatment, engineers must carefully consider well conditions and reservoir characteristics. Specifically, they must analyze
injectivity profiles and perform a multi-rate injection analysis to determine variances in entry that are associated with variances
in injection pressures/rates. The possibility of static condition crossflows that might continue after placement should also be
considered. The profile entry logs generated during these tests are visuals for near-wellbore entry only, and analysts must
always consider the possibility that conditions may differ deeper into the formation. This bullheading option was selected as
being more practical and less expensive for the case histories presented in this paper. The treatments were mixed and pumped
by using a stimulation boat so no additional equipment was required.

Well 1
This is a deviated, cased-hole, offshore well drilled at 12,546 ft (TVD) and completed in a carbonate formation from 14,173 to
14,222 ft MD (49 ft interval). This well started producing in September of 1992 with no water production until 2005, when the
water-oil contact started reaching the perforations (water coning). In April 2008, Well 1 had a production of 4,418 BFPD,
1,902 BOPD, and 2,516 BWPD (57% watercut). The bottomhole temperature for this formation was 290°F. The treatment
consisted of bullheading 189 bbl of seawater spacer, 622 bbl of the OCP system (a theoretical radial penetration of 16 ft),
displaced with seawater. The well was then shut in overnight. This well was reperforated a few feet up from 13,993 to 14,058
ft MD (65 ft interval). Initial production was 2,927 BOPD with no water, as shown in Fig.6. After one year of production, this
well is still showing less than 4% watercut.
SPE 127981 7

Fig. 6—Well 1 wellbore diagram and production history (before and after OCP treatment).

Well 2
This is a deviated, cased-hole, offshore well drilled at 14,114 ft (TVD) and completed in a carbonate formation from 12,234 to
12,277 ft MD (43 ft interval). This well started producing in September of 1993 with no water production until the end of
2005, when the water-oil contact started reaching the perforations (water coning). In June 2007, Well 2 had a production of
4120 BFPD, 1026 BOPD, and 3,094 BWPD (60% watercut). The bottomhole temperature for this formation was 285°F. The
treatment consisted of bullheading 377 bbl of seawater spacer and 201 bbl of the OCP system (a theoretical radial penetration
of 10 ft) displaced with seawater. The well was then shut in overnight. This well was reperforated a few feet up from 12,044 to
12,087 ft MD (43 ft interval). Initial production was 2,060 BOPD with 0.55% watercut, as shown in Fig. 7. After one year of
production, this well is still showing less than 5% watercut.

Fig. 7—Well 2 wellbore diagram and production history (before and after OCP treatment).

Well 3
This is a deviated, cased-hole, offshore well drilled at 14,114 ft (MD) and completed in a carbonate formation from 13,468 to
13,517 ft MD (49 ft interval). This well started producing in September of 1993 with no water production until July of 2006,
8 SPE 127981

when the water-oil contact started reaching the perforations (water coning). In December of 2007, Well 3 had a production of
5429 BFPD, 2325 BOPD, and 3104 BWPD (57% watercut). The bottomhole temperature for this formation was 285°F. The
treatment consisted of bullheading 377 bbl of seawater spacer and 252 bbl of the OCP system (a theoretical radial penetration
of 12 ft) displaced with seawater. The well was then shut in overnight. This well was reperforated a few feet up from 13,106 to
13,172 ft MD (66 ft interval). Initial production was 5,014 BOPD with no water, as shown in Fig. 8. After one year of
production, this well is still showing less than 1% watercut.

Fig. 8—Well 3 wellbore diagram and production history (before and after OCP treatment).

Conclusions
The following conclusions are a result of this work:
• The combination of the OCP and the m-OCP systems has proven successful in controlling water production in the
Caan Field (water coning problems).
• The case histories discussed in this paper used the m-OCP as a tail-in of the main treatment to avoid overdisplacment
of the OCP system in the near-wellbore region caused by the existence of fractures and the low formation pressure.
This combination has become a best practice in this field.
• The OCP system is capable of penetrating deeply into the matrix of the formation to provide a more-effective seal,
particularly for water coning and high-permeability streaks.
• The volume design of the OCP is crucial for the success of the treatment (the more volume injected, the better the
results). This volume becomes even more critical when the problem to be corrected is a combination of water coning
and highly fractured formations.
• The current temperature range of the OCP system is 80 to 350°F (27 to 177°C). To date, more than 600 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.

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
m-OCP Modified- Organically Crosslinked Polymer
OCP Organically Crosslinked Polymer
PAtBA Polyacrylamide t-butyl acrylate
SPE 127981 9

PEI Polyethylenaimine
PPR Percent permeability reduction
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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