Polymer Systems for Water Shutoff and

Profile Modification: A Review Over the

Last Decade
Khalid Saad M. El-Karsani, King Fahd University of Petroleum and Minerals; Ghaithan A. Al-Muntasheri,
Saudi Aramco; and Ibnelwaleed A. Hussein, King Fahd University of Petroleum and Minerals

Summary water contains mercury, arsenic, and other salts (Hibbeler and Rae
Unwanted water production is a serious issue in oil- and gas-pro- 2005). Water is also responsible for most of the corrosion and scale
ducing wells. It causes corrosion, scale, and loss of productivity. problems in the oil field (Donham 1991; Nasr-El-Din 2003; Merd-
One method of treating this problem is to chemically reduce hah and Yassin 2009; Al-Tolaihy and Bukhari 2010). There are
unwanted water. This paper discusses the use of polymer systems mechanical and chemical methods to deal with excessive water
for this purpose and presents a thorough review of available litera- production. The mechanical methods include the application of
ture over the last decade. In this paper, field-application data for particular completion tools, casing replacement, or separation of
various polymer systems are summarized over the range of 40 to produced water by use of hydrocyclones (Vega et al. 2010). Chem-
150 C (104 to 302 F). These applications cover a wide range of ical methods include silicate (Grattoni et al. 2001; Nasr-El-Din
permeabilities from 20 to 2,720 md in sandstone and carbonate and Taylor 2005; Elewaut et al. 2006; Al-Dhafeeri et al. 2008;
reservoirs around the globe. Moreover, the review revealed that Boye et al. 2011), resins (Seright et al. 2003), cements, and poly-
the last decade of developments can be categorized into two major mer gels (Seright et al. 2003; Sydansk 2007; Lightford et al. 2008;
types. The first type is polymer gels for total water shutoff in the Al-Muntasheri et al. 2010). In-situ polymerization was also used
near-wellbore region, in which a polymer is crosslinked with either in the past to shut off water produced through perforations (Saltel
an organic or an inorganic crosslinker. The second type is con- et al. 1999). In this technology, an inflatable setting element is
cerned with deep treatment of water-injection wells diverting flu- used to carry a composite sleeve to the specified perforations zone
ids away from high-permeability zones (thief zones). These thief in the well. The composite sleeve is soft and deformable because it
zones take most of the injected water, which results in a large is made of thermosetting resins and carbon fiber. When the tool is
amount of unrecovered oil. For the total-blocking gels, various set in, heat is supplied to polymerize the resins, and the inflatable
systems were identified, such as polyurethane resins, chromium setting element is deflated and removed. The composite sleeve
(Cr3þ) crosslinking terpolymers, Cr3þ crosslinking foamed par- remains as a hard material inside the casing. Some problems and
tially hydrolyzed polyacrylamide (PHPA), and nanoparticle polye- limitations have been encountered during the application of this
lectrolyte complexes (PECs) sequestering Cr3þ for elongation of technology (Leighton et al. 2001). No new advancements were
its gelation time with PHPA. In addition, polyethylenimine (PEI) captured during the last decade for in-situ polymerization.
was identified to crosslink various polyacrylamide- (PAM-) based Among the chemical methods, polymer gels are considered one
polymers. The Petróleos de Venezuela S.A. (PDVSA) Research of the most commonly applied types because of their relatively low
and Development Center developed a PAM-based thermally stable cost, ease of pumping, and ability to penetrate into the reservoir.
polymer and an organic crosslinker. The system is applicable for a Treatments with polymer gels are generally referred to as conform-
wide temperature range from 50 to 160 C (130 to 320 F). ance-improvement treatments (CITs) (Sydansk et al. 2005). This
For the deep modification of water-injection profiles in water- technology uses a flowable mixture of polymer, crosslinker, and
injection wells, two systems were identified: microspheres water. This mixture of relatively low viscosity (approximately 20
prepared from PAM monomers crosslinked with N,N0 -methylene- cp) is injected into the reservoir. Then, with time and temperature,
bisacrylamide and microspheres produced by crosslinking it forms a physical barrier hindering water production. However,
2-acrylamido-2-methylpropane sulfonic acid (AMPS) with diacry- these treatments do not differentiate oil and gas zones from those
lamides and methacrylamides of diamines (thermally activated producing water. Thus, it is extremely important that the water
microparticles known as Bright Water). This paper highlights all source is identified properly before selecting the treatment method
major developments in these areas. (Bailey et al. 2000; Botermans et al. 2001; Seright et al. 2003;
Sydansk and Seright 2007; Sydansk 2007). In many field cases,
water-producing zones still produce significant amounts of hydro-
Introduction carbons. As such, shutting off these zones completely may not be
Whenever water production exceeds economic limits of a given the right option. In these cases, other polymer technologies exist in
oil or gas field, the need arises for a process by which produced which a polymer is used to decrease the permeability to water more
water is reduced. As of 2000, approximately USD 40 billion was than that to oil (Zaitoun and Kohler 1988; Sydansk and Seright
spent annually to deal with the excessive water produced from oil 2007). This process is referred to as the disproportionate perme-
and gas reservoirs (Bailey et al. 2000; Seright et al. 2003). Publica- ability-reduction effect (Liang et al. 1993, 1995; Botermans et al.
tions that are more recent indicate that this number increased to 2001; Stavland et al. 2006). Polymer gels can also be applied in
USD 45 billion in 2002 (Mercado et al. 2009; Boye et al. 2011). injection wells to improve the reservoir sweep efficiency. This is
Recent cost data are lacking. Data are available on the amount of needed when the water bypasses oil when the injected water flows
produced water. The production of water was reported to be 210 through high-permeability channels or fractures. Deep treatment
million B/D globally in 1999 (Veil et al. 2004). Bailey et al. systems can also be used for improvement of reservoir sweep effi-
(2000) reported the same figure for 2000. This amount increased to ciency. In these systems, microgels are suspended in water and
249 million B/D in 2005 (Khatib 2007). The disposal of produced then injected into the reservoir, where they swell in the presence of
water seriously affects the environment, especially if the produced water deep inside the reservoir (Chang et al. 2002; Lei et al. 2011).

Copyright V
C 2014 Society of Petroleum Engineers Important Factors for Successful CITs
Original SPE manuscript received for review 6 December 2011. Revised manuscript The identification of the water source is a key factor for successful
received for review 8 October 2012. Paper (SPE 163100) peer approved 16 October 2012. CITs. The characterization of water production can be performed

February 2014 SPE Journal 135

 .

CH2 CH .
(Morel et al. 2007). Under high temperatures, PAM undergoes hy-
a drolysis that produces PHPA and ammonia (NH3), as shown in
O C Fig. 2 (Moradi-Araghi and Doe 1987; Moradi-Araghi 2000; Kur-
enkov et al. 2001). This reaction is responsible for the thermal
NH2
instability of the produced gel. To enhance the thermal stability of
PAM, other groups are incorporated into the polymer backbone,
such as vinyl pyrrolidone (VP) (Fig. 3) and methylpropane sul-
Fig. 1—Chemical structure of PAM (Kurenkov et al. 2001).
fonic acid (Fig. 4). One more way of addressing thermal stability
is the use of higher polymer loading (up to 5 wt%) (Sydansk and
Southwell 2000). Crosslinkers can be inorganic [such as Cr3þ
through different methods. A submersible pump can give an ob-
(Sydansk 1990)], organic [such as PEI (Hardy et al. 1999)]
servation for the increase in water cut. Any increase in water/oil
(Fig. 5), or natural [such as chitosan (Reddy et al. 2003)] (Fig. 6).
ratios (WORs) is a clear indication about excess water production.
During the last decade, various new chemical properties were
In addition, plots of production as a function of time can be used
introduced, as well as modifications of existing products by add-
to assess the WORs. The water production can also be estimated
ing strengthening components. Two types of polymer systems are
by reservoir-simulation analysis (Seright et al. 2003).
reviewed in this paper: systems for treating water problems near
Seright et al. (2003) gives comprehensive strategies for
the wellbore region and systems for deep profile modification.
addressing excess water production and suitable treatments. For
Fig. 7 gives an overview of the technologies reviewed in this
the problems with flow behind pipes, cement alone could not
paper.
solve the problem because of its limited penetration into the rock
For inorganically crosslinked gels, foam was combined with
matrix. Thus, cement, sand plugs, carbonate squeezes, and gels
PHPA/Cr3þ gels to treat deep wormholes in Canada (Asghari
can be used to treat excess water production in unfractured wells
et al. 2005). Advances in nanotechnologies were used to elongate
with crossflow. Although gel treatments showed a wide success in
the gelation time of PHPA/Cr3þ gels by sequestering the Cr3þ
treating water production, gels will not be successful with some
(Cordova et al. 2008). Moreover, PHPA produced from PAM ter-
difficult and complicated water problems. These problems include
polymers were tested for crosslinking with Cr3þ (Prada et al.
3D coning, cusping, and channeling through layers (unfractured)
2000). Colloidal dispersion gels (CDGs) are based on PHPA
with crossflow.
crosslinked by aluminum citrate (Al-Assi et al. 2009). Chromium
In addition to identifying the source of water in a certain oil-
triacetate was also used as a crosslinker to form CDGs in many
or gas-producing well, other factors are important to consider
applications in Argentina (Diaz et al. 2008). The formulated
while designing these treatments. First, the gel must be thermally
CDGs are suspended in solution as colloids. The gel structure
stable, maintaining a reasonable physical structure over extended
requires low polymer concentration and longer forming time com-
periods of time (from 6 months to 2 years) (Moradi-Araghi 2000).
pared with bulk gels. CDGs were reported for use in modification
Gelation time is also an important factor. In matrix treatments, it
of water-injection profiles. There has been a controversy on the
must be long enough so that the gel can penetrate into the reser-
propagation of CDGs deep into the rock matrix. In a field pilot
voir to ensure sufficiently deep placement. Various factors affect
study by Chang et al. (2006), it was reported that the injection of
gelation time, such as temperature, salinity of mixing water, con-
CDGs resulted in increasing the residual resistance factor. It was
centrations of polymer, crosslinker, and pH value of the mixed
explained that CDGs created a resistance deep in the reservoir
fluid. Hence, proper laboratory testing must consider all these fac-
without any plugging in the near-wellbore region. The authors did
tors when tests are performed with representative samples of mix-
not provide legitimate evidence for this claim. Spildo et al. (2009)
ing waters from the concerned fields.
hypothesized that the increase in oil recovery by CDGs is caused
Moradi-Araghi (2000) gives a comprehensive review on gel
by an increase in microscopic diversion because of the blocking
chemistry for water control. Kabir (2001) also gives another
of pore throats by those aggregates. Al-Assi et al. (2009) studied
review on chemical systems for water- and gas-shutoff systems.
the propagation of CDGs in sandpacks with a permeability of 10
Jaripatke and Dalrymple (2010) discussed the diagnosis of water
darcies. The penetration of CDGs was found to be limited to a
problems as well as developments in the technologies used to
short distance because of the retention of these particles. More
solve those problems. These reviews did not give detailed field-
studies of CDGs propagation showed that once the crosslinking
application data or chemistry information for the treatments
occurs, the PHPA/Al3þ complexes (i.e., those larger than pore
reviewed. Sydansk and Romero-Zeron (2011) give a broad review
throats) will not propagate through porous rock (Seright 2007).
about gel treatments, but some advancements were not captured.
For this reason, we are reporting CDGs under the treatments of
To the best of our knowledge, since 2000, no paper has provided
the near-wellbore region. The paper will discuss these advances in
a thorough review on the development of polymer systems for
Cr3þ crosslinked gels as well as CDGs (PHPA/Al3þ).
water shutoff and their chemical properties, despite the fact that a
For the organically crosslinked gels, several systems were
good number of publications were devoted to various technolo-
identified in this review. Polyurethane resins produced from iso-
gies of water shutoff. Thus, the objectives of this paper are to pro-
cyanate/alcohol reactions were tested for application in Petronas
vide a thorough review on available polymer systems for total
fields in Malaysia (Shafian et al. 2010). The system has a control-
water shutoff and modification of water-injection profiles, high-
lable gelation time because of the use of blocking materials that
light advantages and shortcomings of these technologies, and
do not expose the isocyanate to the reaction with alcohol until a
summarize the field experience with these systems.
certain temperature is reached. The PDVSA Research and Devel-
opment Center developed a gel system that was derived from a
Discussions thermally stable PAM polymer and an organic crosslinker. Differ-
PAM has been extensively used in preparing polymeric gels (Fig. 1). ent versions of this system were formulated depending on the
It is a cost-effective polymer (approximately USD 2 to 4/kg) temperature of the target zone. The PAM tert-butyl acrylate

CH2 CH CH2 CH NaOH CH2 CH CH2 CH

O C O C + NH3
O C O C

NH2 NH2 O– NH2

Na+

Fig. 2—Hydrolysis of amide groups under alkaline conditions (Moradi-Araghi and Doe 1987; Moradi-Araghi 2000; Kurenkov et al.
2001).

136 February 2014 SPE Journal

 CH2 CH CH2 CH
.

CH2 CH CH2 CH .

x y x y

O C O C NH2
N O C
O NH

NH2 CH3 C CH3

H2C
Fig. 3—Chemical structure of PAM VP (Moradi-Araghi 2000).
SO3H

NRR'
Fig. 4—Chemical structure of acrylamide/AMPS copolymer (Al-
Muntasheri 2008).
H2 C

CH2 reservoir. The microparticles should be injected and swell first in

x the high-permeability zones after passing the thermal front. This
NR results in diverting the injected water to less-swept zones (low-
permeability zones), and additional oil could be recovered (Chang
CH2 et al. 2002; Ohms et al. 2010). Aggregate gels rooted in the cross-
linking of acrylamide monomers with N,N0 -methylenebisacryla-
H2C mide crosslinker were also introduced in the past decade for deep
modification of water-injection profiles (Lei et al. 2011). These
authors reported that these aggregates have small size (5 to 25
NRR' lm) with large storage and loss moduli. As such, their propaga-
tion was attributed to the elasticity of these aggregates; the
Fig. 5—Chemical structure of PEI (Hardy et al. 1999). authors reported that these aggregates deform and recover their
shapes when passing through the pore throats. However, the
(PAtBA) crosslinked with PEI was modified by adding such measured elasticity moduli were not compared with those of other
strengthening materials as cement, silica flour, and rigid-setting systems. All these systems along with their available field-appli-
materials (RSMs). Reddy et al. (2003) reported that according to cation data will be discussed in the following subsections. Some
European environmental regulations, a phase out of PEI from the of these systems were applied in the field, whereas others were
Norwegian sector of the North Sea was planned. Thus, alterna- tested only in the laboratory (Table 1). Moreover, some systems
tives to PEI were sought. Chitosan was found to be a good alterna- were applied in production wells for water shutoff, whereas others
tive for PEI because it contains amino groups to react with were designed for in-depth profile modification in water-injection
acrylamide-based polymers in the manner of PEI. At the same wells (Table 2).
time, it is a bioproduct with no environmental concerns. Research
was also devoted to examining polymer chemical properties and Developments in PHPA Crosslinked With Cr31. PHPA cross-
to using simple PAM homopolymers to replace PAtBA. There linked with Cr3þ was first introduced in 1990 (Sydansk 1990).
was no technical reason for this trend other than the lower cost of The gel is created on the basis of coordination covalent bonding
PAM compared with that of PAtBA. High-temperature applica- between Cr3þ and the negatively charged carboxylate groups on
tions forced the use of chemical retarders to elongate the gelation the PHPA (Sydansk 2007). PHPA structure is shown in Fig. 2 as a
time of these gels. An overview of these retardation chemicals product of the hydrolysis reaction. To improve the thermal stabil-
will be given in this paper. ity of this gel, Sydansk suggested the use of higher polymer load-
For the deep modification of water-injection profiles, the paper ings (5 wt%) and a low-molecular-weight PHPA (approximately
identified two systems: Thermally activated microparticles and 270,000) with a low degree of hydrolysis. More literature reports
nanospheres. The thermally activated microparticles represent a are available to discuss PHPA thermal stability (Moradi-Araghi
microparticle-based system that can be injected with water. Its et al. 1987; Lockhart 1991; Albonico et al. 1994). Over the past
density is similar to that of water, and it therefore has minimum decade, three new advancements of this system were cited in the
gravity segregation in the reservoir during its propagation (Pritch- literature, and they will be discussed in the following subsections.
ett et al. 2003). These particles expand with temperature and time These advancements include laboratory tests only and have not
to block the high-permeability zones (thief zones). Because yet been applied in the field. Table 3 provides a summary of the
microparticle swelling needs to be activated by high temperature, developments in this section for Cr3þ-crosslinked gels.
the working mechanism of these particles in the reservoir could Nanoparticles for Retardation. To increase the gelation time,
be explained by the thermal-front concept (Seright et al. 2011). A nanoparticle PECs were introduced by Cordova et al. (2008) and
thermal front is created by injecting cold water into a hot or warm Berkland et al. (2010). The system was created from PHPA, Cr3þ,

OH
H
OH
H H
O
H OH
O O H
H
HO O O
H NH2 HO O
H H NH2
HO O
H H H NH2
H H
H

Fig. 6—Chemical structure of chitosan (Reddy et al. 2003).

February 2014 SPE Journal 137

 Water Shutoff
Chemicals

Polymer Gels for Near Microgels for Deep

Wellbore Area Profile Modification

Organically Inorganically AM/N,N´

Cross-linked Cross-linked Methylene
Gels Gels bisacrylamide
Aggregates

PHPA/Cr+3 Bright Water

PAtBA/PEI PAM/PEI
Foam

PHPA/Cr+3
PDVSA Gel AMPS/PEI
Nano-
particles

AMPS/N,N’ -
DMA PHPA/Chitosan
PHPA from
copolymer/PEI
terpolymer/
Cr+3

Polyurethane
PAtBA/Chitosan
Resins
Colloidal
Dispersion
Gels

Fig. 7—Overview of the available technologies reviewed in this paper.

PEI, and dextran sulfate (DS). PEI and DS form a particle, with a tilled water, the gelation time was less than 30 minutes at 40 C
diameter ranging from 100 to 200 nm, that sequesters the Cr3þ. (104 F). Upon the addition of nanoparticles, the gelation time
At these conditions, the gelant will be a stable colloid. The increased to 7 days under the same conditions. It should be noted
sequestration of Cr3þ in these particles delays the gelation reac- that the authors observed precipitation of salts upon the use of
tion. Johnson et al. (2010) studied the effect of divalent cations high concentrations of Mg2þ and Ca2þ. Mg2þ was found to delay
such as Ca2þ and Mg2þ, as well as seawater and field water, on the gelation time further compared with Ca2þ. The authors
gelation time when using PEI/DS/Cr3þ nanoparticle PECs. In dis- observed a gelation time of approximately 9 hours at 40 C

TABLE 1—LABORATORY-TESTED AND FIELD-APPLIED CLASSIFICATION FOR THE VARIOUS

POLYMER SYSTEMS REPORTED IN THIS PAPER

Laboratory Field
System Tested Proven

PDVSA-Intevep polymer-gel system Yes Yes

Polyurethane resins from isocyanate fluids Yes No
PAM PAtBA/PEI Yes Yes
PAtBA/PEI, with cement Yes Yes
PAtBA/PEI, with silica flour Yes Yes
PAtBA/PEI, with rigid-setting material Yes Yes
Acrylamide/AMPS/PEI Yes No
Mixtures of acrylamide/AMPS and N,N-dimethyl-acrylamide/PEI Yes No
PAM/PEI Yes No
PHPA/chitosan Yes No
PDVSA-Intevep polymer-gel system Yes Yes
PAtBA/chitosan Yes No
PHPA/sequestered Crþ3 by polyelectrolyte nanoparticles Yes No
Foam PHPA/Crþ3 Yes No
Terpolymer of acrylamide, acrylate, and AMPS/Crþ3 Yes No
Acrylamide monomers crosslinking N,N0 -methylenebisacrylamide Yes No
Acrylamide monomers crosslinking N,N0 -methylenebisacrylamide Yes Yes
preformed particle gel (PPG)
Thermally activated microparticles (Bright Water) Yes Yes
CDGs Yes Yes

138 February 2014 SPE Journal

 TABLE 2—WELL TYPES WHERE THE POLYMER SYSTEMS WERE APPLIED

Polymer System Well Type

CDGs Injection
PDVSA-Intevep polymer-gel system Production
PAtBA/PEI Production
PAtBA/PEI, with cement and silica floor Production
PAtBA/PEI, with rigid-setting material Production
PAtBA/PEI, with chemical retarder Production
Acrylamide monomers crosslinking N,N0 -methylenebisacrylamide Injection
Thermally activated microparticles (Bright Water) Injection

(104 F) and 0.08 mol/kg of divalent cations. It increased to PHPA crosslinked with aluminum citrate. The gel formed is sus-
approximately 18 days after increasing the divalent-cation con- pended in solution as separate bundles or colloids, hence the
centration to 0.18 mol/kg. This system is newly introduced and name CDG. Compared with bulk gels, which require high poly-
has yet to be applied in the field. mer concentration (approximately 5,000 ppm), lower polymer
Foam Gel. Foam gel was also developed to block wormholes concentrations (approximately 100 to 1,000 ppm) are needed to
in the Lloydminster region of Canada (Asghari et al. 2005). These form the gel network in CDGs (Spildo et al. 2009). Increasing the
wormholes were the result of producing sand through the process molecular weight and concentration of PHPA was found to
of cold heavy-oil production with sand. The wormholes resulted in increase the size of CDGs (Li et al. 2004). At the same time, intra-
excessive water production in the subject field. The authors pro- molecular crosslinking in CDGs is dominant over intermolecular
posed the use of foam gel on the basis of crosslinking PHPA with crosslinking. Moreover, the time needed to complete CDG forma-
Cr3þ along with a surfactant. Nitrogen gas is added to produce the tion was found to be higher than that required for bulk gels. The
foam. The advantage of this foam system over conventional gel reaction time was observed to be 7 days at 40 C (104 F) (Li et al.
treatments is that it uses lower amounts of gelant, thus significantly 2004). Bjørsvik et al. (2008) studied the formation of CDGs. The
reducing treatment costs. To provide adequate foam stability in particle size of the CDGs was found to be approximately 50 nm.
this high-permeability application, the authors used two surfac- In another study, the size of the CDGs was reported to be within
tants (main and a cosurfactant). A setup for testing the perform- the range of 1 to 100 nm (Spildo et al. 2009). The propagation of
ance of the system for reducing the brine permeability had a high- CDGs into rock matrix has been controversial. Chang et al.
permeability wormhole between two sand layers. Wormholes had (2006) speculated that CDGs propagate a long distance into a res-
different sizes. Injecting 1 cm3/min of the gel system in a worm- ervoir and provide a resistance factor greater than a polymer with-
hole with 0.7-cm thickness reduced the permeability to brine from out a crosslinker. All legitimate available studies prove that once
777 to 1.67 darcies. When increasing the size of the wormhole to the crosslinking takes place, the PHPA/Al3þ complex, which has
3.7 cm, the brine permeability was reduced from 92 to 0.215 dar- larger size than pore throats, will not propagate through porous
cies with the same flow rate. This foam gel technology is still in media (Seright 2007). Spildo et al. (2009) studied the propagation
the research phase and has not been tested in the field. of CDGs in real cores from a North Sea sandstone oil field. The
PHPA From Terpolymers. Prada et al. (2000) studied a poly- permeability of the cores is within the range of 100 to 1,000 md.
mer system based on a terpolymer of acrylamide, acrylate, and The coreflooding tests were conducted at 85 C (185 F). After
AMPS (approximately 3 to 5 million Daltons) crosslinked with injecting the CDGs, a decrease in residual oil saturation was
Cr3þ. The temperature limit for this system was 60 to 121.1 C noticed. Unlike the previous studies on CDGs at low temperature
(140 to 250 F). However, a coreflooding test was performed only and low salinities (approximately 5,000 ppm), the study by Spildo
at a low temperature of 140 F (60 C) by use of two cores with et al. (2009) revealed that CDGs could be prepared at high tem-
water permeabilities of 2,720 and 1,145 md. The final permeabil- perature of 85 C (185 F) and high salinity (approximately 35,000
ities were observed to be 450 and 10 md, respectively. The result- ppm). It should be noted that use of low-salinity waters for CDG
ing gel had a moderately deformable nonflowing structure. The preparations leads to faster crosslinking and higher strength
authors did not report gelation-time data for this system. (Chang et al. 2006).
Mack and Smith (1994) reported the first field-application data
for CDGs. The incremental oil recoveries ranged from 1.3 to
CDGs. In heterogeneous reservoirs, in which the permeability 18.2%. Chang et al. (2006) reported about a more recent applica-
variations cover a wide area, large volumes of gels should be tion of CDGs in Daqing oil field, China. The reservoir is sand-
injected for in-depth permeability correction. Injection of gel as stone with low salinity (5,000 to 7,000 ppm) and a temperature
bulk was found to have some drawbacks. Producing strong bulk near 45 C (113 F). The average water cut before the injection of
gels required high polymer and crosslinker concentrations, which CDGs was 95.2%. The post-treatment data showed that the maxi-
are unfavorable from an economic point of view. In addition, fast mum decrease in water cut was 19.8%. The incremental oil recov-
crosslinking makes in-depth placement difficult to achieve. On ery was found to be 10.5%, which was above the planned value
the other hand, it is difficult to control the gelation if the polymer (9.0%). A trial was made to inject CDGs in a well with a watered-
and crosslinker are injected separately (sequential injection). out zone. The water cut was reduced from 98 to 91%, and the oil
CDGs were touted as overcoming these drawbacks. CDGs are production increased from 1 to 3 tons/D. The authors used this

TABLE 3—SUMMARY OF DEVELOPMENTS IN CHROMIUM-CROSS-LINKED GELS

Temperature Range
System for Laboratory Tests (C) Reference

PHPA/Sequestered Crþ3 by polyelectrolyte nanoparticles 40–80 Cordova et al. 2008; Johnson et al. 2010
Foam PHPA/Crþ3 30 Asghari et al. 2005
Terpolymer of acrylamide, acrylate, and AMPS/Crþ3 60–121.1 Prada et al. 2000

February 2014 SPE Journal 139

 TABLE 4—SUMMARY OF ORGANICALLY CROSSLINKED GELS

System Temperature Range (C) Field Application Reference

PDVSA-Intevep polymer-gel system 54–160 Reduced water cut, down Perdomo et al. 2007
to zero in some cases
Polyurethane resins from isocyanate fluids 95–120 No field application Shafian et el. 2010
PAtBA/PEI Up to 176 Reduced water cut, down Vasquez and Eoff 2010
to zero in some
applications
PAtBA/PEI, with cement 118–144 Reduced water cut, from Van Eijden et al. 2004
63 to 25 %
PAtBA/PEI, with silica flour Up to 150 Total sealing Van Eijden et al. 2005;
Dalrymple et al. 2008
PAtBA/PEI, with rigid-setting material 204 Total sealing Deolarte et al. 2009
Acrylamide/AMPS/PEI 132–177 No field application Vasquez et al. 2003
Mixtures of acrylamide/AMPS and Up to 135 No field application Vasquez et al. 2005
N,N-dimethyl-acrylamide/PEI
PAM/PEI 130 No field application Allison and Purkaple 1988;
Al-Muntasheri 2008
PHPA/chitosan Up to 65.5 No field application Reddy et al. 2003
PAtBA/chitosan 65.5–121.1 No field application Reddy et al. 2003

finding to conclude that CDGs are not operative in fully watered- permeability modifier (RPM) or a total blocking gel at high-tem-
out zones. CDG was also applied in Grupo Neuquen Formation, perature applications. There are no data supporting their claim
Argentina (Diaz et al. 2008). The reservoir is heterogeneous mul- about using the system as an RPM. Perdomo et al. (2007) reported
tilayered sandstone with a temperature of 45 C (113 F) and a per- that this system was able to withstand 5,000 psi of differential
meability ranging from 20 to 1,000 md. Chromium triacetate was pressure. The chemistry of this system was not published in any
used as a crosslinker instead of aluminum citrate. The injection of patent or paper (personal communication with M.I. Hernandez.
186,000 bbl of CDGs resulted in an incremental oil recovery of 2012. YPF-Tecnologia. Buenos Aires.)
approximately 21 194 m3 (133,292 bbl), which represents 2.9% of The system was implemented in different fields in Venezuela.
the original oil in place. Different water-production problems were treated by this system,
There has been a longstanding controversy about the propaga- such as high-permeability channels and flow behind casing. The
tion of CDGs and their effectiveness over uncrosslinked polymer. system was applied in a sandstone reservoir with a permeability
Some questions were raised and still wait for answers. Specifi- ranging from 20 to 3,000 md and a temperature from 90 to 150 C
cally, why should the CDGs not enter and plug low-permeability (190 to 310 F). Table 5 shows a detailed description of the field
zones as well as high-permeability zones? How will the CDGs results in different parts of Venezuela.
propagate deep into the reservoir? Generally, a legitimate scien- Polyurethane Resins From Blocked Isocyanate Fluids.
tific and engineering basis for the propagation of CDGs has not Polyurethane is used as a coating material for offshore equipment
been established yet. to protect against corrosion (Park et al. 2009; Son et al. 2010). It
is a strong polymeric material with good adhesion properties. Sha-
Developments in Organically Crosslinked Gels. The literature fian et al. (2010) reported on the use of polyurethane for water
review revealed that there are several new advancements in the shutoff. The system was designed for use in Petronas fields as a
area of organically crosslinked gels. The following subsections sealant. The application of this system may face some environ-
will give an overview of these developments. Table 4 gives a mental regulations because isocyanate is toxic and explosive and
summary of the information presented here. requires special handling. The chemistry of this system is based
PDVSA-Intevep Gel System. The PDVSA Research and De- on the isocyanate group (–N¼C¼O), which has a blocking mate-
velopment Center has developed a polymeric gel to meet the rial, making it unreactive; isocyanate reaction with alcohol cannot
high-temperature conditions of Venezuelan fields. This polymer be controlled to provide adequate gelation delay. Then, as the
gel has been developed in different formulations depending on the temperature increases to 90 C (194 F) and above, the isocyanate
target zone temperature [130 to 320 F (50 to 160 C)]. The system group becomes active and reacts with polyalcohol groups to form
is based on a thermally stable water-soluble polymer and an or- polyurethane (Petrie 2001; Shafian et al. 2010). This reaction is
ganic crosslinker. The elasticity and gelation time of this system illustrated in Fig. 8. Coreflood tests were carried out to evaluate
can be highly controlled, which makes it applicable as a relative the injectivity of this system into Berea cores at three different

TABLE 5—SUMMARY OF FIELD RESULTS FOR PDVSA-INTEVEP POLYMER-GEL SYSTEM APPLIED IN VENEZUELA

Water-Production
Field Location Mechanism Application Results Reference

Southern Venezuela High-permeability WOR reduced from 16 to 0.11; oil production Prado et al. 2005
channels increased from 170 to 450 BOPD
Lake Maracaibo Basin Channeling and flow WOR reduced from 4 to 0.05 (channeling), Der Sarkissian
behind casing and from 6.4 to 1 (flow behind casing); oil et al. 2005
production increased by more than 100%
North Mongas Channeling through WOR reduced from 0.639 to zero; oil pro- Perdomo et al.
(El Furrial field) formation duction increased by more than 100% 2007

140 February 2014 SPE Journal

 H O CH CH2 CH
CH2

R' N C O + R OH R' N C OR
O C O C

Urethane O NH2

Fig. 8—Urethane synthesis by reacting isocyanate with alcohol C

H3C CH3
(Petrie, 2001; Shafian et al. 2010).

CH3
temperatures: 80, 95, and 120 C (176, 203, and 248 F, respec-
tively). Their results indicated that the injectivity at 80 C (176 F) Fig. 9—Chemical structure of polyacrylamide t-butyl acrylate
is easier than at 95 and 120 C (203 and 248 F, respectively). (PAtBA) (Al-Muntasheri and Zitha 2009).
When the gel was cured for 36 hours at 80 C (176 F), no water
breakthrough was noticed after applying 900-psi differential pres-
sure across 6-in. cores. The same results were noticed at 95 and Gel-Strength Enhancement by the Use of Cement and Silica
120 C (203 and 248 F, respectively) under the same conditions. Flour. To enhance the strength of PAtBA/PEI system, other
An aging test was conducted at 95 C (203 F) for a long period materials were added to the gelling recipe. Van Eijden et al.
(ranged from 1 to 3 months), and the system showed good shutoff (2004) investigated the use of cement as an additive to the
with low water breakthrough. In fact, the system was able to PAtBA/PEI system. The objective was to use the modified gel
reduce the permeability in Berea cores from 30.5 to 0.11 md, with the extra strength to seal the lower perforations of oil pro-
showing 99.6% reduction when aged for 1 month, although this ducers. This option was more cost-effective compared with use of
reduction dropped to 81% after 3 months. The authors did not pro- a workover rig as a mechanical solution, which requires casing
vide reasons for the decreasing trend in water-shutoff efficiency. replacement. The addition of cement can give a robust perforation
This system has not been applied in the field yet. Data are avail- shutoff, whereas the gel will be responsible for the rock-matrix
able only as laboratory tests. shutoff. This modified version of PAtBA/PEI was applied in two
Advances in the System of PAtBA Crosslinked With oil-producing wells with bottomhole temperatures of 118 and
PEI. The System of PAtBA Crosslinked with PEI. The PAtBA/ 144 C (244 and 291 F, respectively). In the first well, with 118 C
PEI gel system was introduced before 2000 by several researchers (244 F), the well was producing a total of 3,000 BOPD at a water
(Morgan et al 1997; Hardy et al. 1998; Urlwin-Smith 1998, 2001) cut of 63%. After the treatment, the increase in oil rate ranged
as a sealant for water in petroleum reservoirs. The chemical struc- from 4,000 to 4,500 BOPD. At the same time, the water cut was
tures of PEI and PAtBA are shown in Figs. 5 and 9, respectively. reduced to 25%. However, the water cut increased from 25 to
PAtBA has 4.7 mol% of tert-butyl acrylate (tBA) groups; this is 55% over a period of 1 year. The treatment for the second well
referred to as the degree of esterification of the PAtBA. Two was not successful. Van Eijden et al. (2005) developed another
mechanisms were proposed for this reaction, including a transa- system, which is an extension of the gel/cement system. This was
midation reaction at the amide nitrogen of the PAM part and a developed to meet the high-temperature condition of wells in Syr-
nucleophilic attack on the carbonyl carbon of the tBA part by an ian fields (150 C or 302 F). Use of retarders with the gel in the
imine nitrogen. These mechanisms are shown in Figs. 10 and 11, cement/gel system did not elongate the gelation time, because
respectively. Al-Muntasheri et al. (2006) provided a detailed cement interacted chemically with the retarders. The chemical na-
investigation of the mechanisms of the PAtBA and PEI. This sys- ture of these interactions was not known. At 10 wt% of cement,
tem was applied widely in various parts of the world (Uddin et al. interactions were not noted. Thus, the authors used a maximum of
2003; Polo et al. 2004; Eoff et al. 2006; Vasquez et al. 2006; June- 10 wt% of cement to provide more strength, whereas the rest of
sompitsiri et al. 2009; Vasquez and Eoff 2010). the solid material was silica flour. Silica flour was selected

n n
n n NH2 NH
NH C O O
C
C O C O + N n
NH N
RX RX NH
N n
NH2

NH2

Fig. 10—Crosslinking through transamidation reaction [X5O, N; R5NH2, N (CH3)2] (Hardy et al. 1999; Vasquez et al. 2005).

n n
n n NH2 NH
NH C O O
+ n C
C O C O N
NH N
RX RX NH
N n
NH2

NH2

Fig. 11—Crosslinking through nucleophilic attack [X5O, N, R5C(CH3)3, C(CH3)3, CH2SO3H] (Hardy et al. 1999; Vasquez et al. 2005).

February 2014 SPE Journal 141

 converted into amides. This is referred to as derivatized PEI
TABLE 6—SUMMARY OF CHEMICAL RETARDERS REPORTED (Hardy 2001). As a result, these groups will take time to be con-
FOR THE PAtBA/PEI SYSTEM verted into active sites for crosslinking. Another retarder for the
PAtBA/PEI system was a polyamino acid. The working mecha-
Maximum nism for this retarder is believed to be by forming a complex with
Retarder Type Temperature ( C) Reference the crosslinker (PEI). As a result, this complex will hinder the
Derivatized PEI 177 Hardy et al. 2001;
imine groups attack on the polymer. This will in turn increase the
Vasquez et al. 2005 gelation time.
Sodium carbonate was also reported as a retarder for the
Polyamino acid 135 Vasquez et al. 2005
PAtBA/PEI system. The mechanism for elongating gelation time
Sodium carbonate 177 Eoff et al. 2006
by sodium carbonate is believed to be an interaction between the
Sodium chloride 127 Al-Muntasheri et al. 2010 positively charged sodium ion with the carboxylate groups result-
Ammonium chloride 150 Al-Muntasheri et al. 2011 ing from the hydrolysis of PAtBA, thus reducing the sites avail-
able for crosslinking and consequently increasing the gelation
time. Eoff et al. (2007) extended the working temperature of the
PAtBA/PEI system to 176.7 C (350 F) by the use of this retarder.
because of its availability, cost-effectiveness, and inert behavior
After doing a sandpack flow test, the authors concluded that the
with respect to the gel chemistry. Note that the total amount of
addition of this salt as a retarder could raise the working tempera-
solids in the gelant was 51 wt% (including 10 wt% cement). The
ture without affecting the gel strength and its subsequent ability to
field tests indicated that the system without cement was washed
stop fluid flow.
out by use of coiled tubing. The gel was squeezed into a long per-
Sodium carbonate has disadvantages when used with high-sa-
foration interval of 186 m and provided a total sealing capability.
The authors did not report final oil and water rates after this treat- linity brines. A recent study of PAtBA/PEI gel was reported in
ment. Dalrymple et al. (2008) reported gelation-time measure- which the gel was considered for a high-temperature reservoir in a
ments of the PAtBA/PEI system with and without silica flour; the horizontal well with a bottomhole temperature of 300 F (149 C)
two measurements gave approximately the same time, and the in Saudi Arabia (Al-Muntasheri et al. 2010). Sodium carbonate
authors used that finding as a confirmation of the inert behavior of was found to be incompatible with the formation brine of the sub-
silica flour with respect to the gelation reaction. ject field and the mixing brines. The authors attempted the use of
PAtBA/PEI With RSM. Deolarte et al. (2009) reported the sodium chloride, but its retardation effectiveness was below
application of PAtBA/PEI along with another additive referred to expectations. Thus, it drove further research to look for a new
as RSM. This system was developed as a sealing gel to treat water- retarder that was cost-effective, efficient, and compatible with the
coning problems in the Cantarell field in Mexico. The PAtBA/PEI available mixing brines. The retarder (ammonium chloride) gave
was proposed to treat the formation matrix. In such a scenario, the a gelation time of 1.5 hours at 150 C (302 F). The treatment was
near-wellbore region will be left untreated because the gelant will performed on a dead gas well. After the treatment, the well
penetrate deep into the reservoir before it forms the 3D structure. showed a 46% water-cut reduction and produced 17 times more
Hence, water finds its way quickly into the wellbore. This water gas. Al-Muntasheri et al. (2011) report the chemistry of this
entry was the experience in the subject field until the RSM was retarder. Table 6 gives a summary of the retarders available for
introduced to overcome this challenge. The RSM is a metal oxy- the PAtBA/PEI system.
chloride-type cement that is thermally stable up to 400 F (204 C) New Polymers Crosslinked With PEI. The Acrylamide/
(Barclay et al. 2006). Although this material is designed to give a AMPS Copolymer Crosslinked With PEI. Another polymer sys-
low-viscosity fluid, its setting time into a solid is very short. Thus, tem, based on acrylamide and AMPS crosslinked with PEI, was
it seals the near-wellbore region immediately. The technology was developed to address challenges associated with high tempera-
applied in various wells in the subject field. We will give two tures and to avoid the use of retarders and preflush fluids (Vasquez
examples. The candidate well in the Cantarell field had a perme- et al. 2003). In this case, the crosslinking is believed to be delayed
ability of 1,710 md. It was completed in a carbonate reservoir with because of the steric hindrance provided by the bulky methylpro-
a bottomhole temperature of 225 F (107 C). After treatment, the pane and sulfonic acid groups on the polymer (Fig. 4). The gela-
well produced an extra 1,325 BOPD for a period of 1 year. Another tion time was measured for this system through visual observation
candidate well was treated with the same technology. It had a per- in a laboratory test by use of sealed tubes. The results showed a
meability of 2,512 md with a bottomhole temperature of 222 F gelation time ranging from 2 to 20 hours over the temperature
(105 C). The gel/RSM system was used to seal the lower interval range from 132.2 to 176.7 C (270 to 350 F) by varying the con-
and the old perforations. Then, an upper interval in the same for- centration of the polymer and crosslinker. No literature reports
mation was perforated to produce dry oil. After the treatment, the highlight a field application with this system.
well produced 12,800 BOPD at a zero water cut. Mixtures of Acrylamide/AMPS and N,N-Dimethyl-acrylam-
Chemical Retardation Systems for the PAtBA/PEI Gel. ide N,N Crosslinked With PEI. Further efforts were continued to
High-temperature reservoirs require the use of a method to elon- develop new polymer chemical properties for high-temperature
gate the gelation time of the gelant. This is to avoid premature ge- applications. A mixture of acrylamide, AMPS, and N,N-dimethyl-
lation and to ensure deep penetration of the gelant. One method is acrylamide N,N crosslinked with PEI was studied by Vasquez
to use preflush to cool down the near wellbore region. This et al. (2005). This system was reported to be stable up to a tem-
method can drop the temperature by approximately 30 C (54 F) perature of 177 C (350 F). The gelation time at 135 C (275 F)
(Al-Muntasheri et al. 2010). In several cases, it might be unac- was found to be 23 hours at a PEI concentration of 1 wt% using
ceptable to inject greater amounts of water into oil zones, and in this mixture. Moreover, an increase in gelation time up to 41
some reservoirs, the injection of small amounts of water can sig- hours was noticed at the same temperature by use of a polymer
nificantly alter the effective permeability to oil (Morgan et al. concentration of 5 wt%. This system achieved a 97% reduction in
1997). Another method to elongate the gelation time is to alter the water permeability for 1 year. However, no field application data
crosslinker’s chemistry to reduce its activity during injection. In were reported to verify its performance in the reservoir.
addition, a chemical retarder can be used. The retarder affects the PAM Crosslinked With PEI. Allison and Purkaple (1988)
chemistry of the gelation reaction and elongates the time it takes published the first study of PAM crosslinked with PEI. These
the gel to form. Various retardation chemicals were introduced in authors observed aqueous gels upon the crosslinking of PAM with
the literature over the past several years. In this subsection, we PEI at room temperature. Al-Muntasheri et al. (2006) investigated
will shed light on these technologies. the gelation mechanisms of PAtBA/PEI and concluded that cross-
Vasquez et al. (2005) reported on a different form of PEI to linking can still take place at the amide groups of the PAtBA—
elongate gelation time. In this form, the amine groups have been eliminating the need for the ester groups. Al-Muntasheri et al.

142 February 2014 SPE Journal

 TABLE 7—MICROGELS FOR DEEP MODIFICATION OF WATER-INJECTION PROFILES

Temperature Particle
for Laboratory Diameter
System Tests ( C) (lm) Reference
0
Acrylamide monomers crosslinking N,N -methylenebisacrylamide 55 0.05 Wang et al. 2010
Acrylamide monomers crosslinking N,N0 -methylenebisacrylamide PPG 87.8 10–30 Lei et al. 2011
Thermally activated microparticles (Bright Water) 95 0.5 Frampton et al. 2004

(2008) investigated the gelation kinetics and thermal stability of 2009). These microspheres also swell in the presence of water,
the PAM/PEI system. The system showed rigid stable gels for 8 thought to provide a deep reservoir treatment to allow a better
weeks at 130 C (266 F) with polymer and PEI concentrations of sweep efficiency by improving the injection profiles in water-
7 and 1 wt%, respectively. The authors investigated the effect of injection wells. The system is prepared by mixing acrylamide
salts and found that sodium chloride increased the gelation time monomer, N,N0 -methylenebisacrylamide (organic crosslinker),
from 0.67 hour (in distilled water) to 4.4 and 6.8 hours by adding and ammonium persulfate (initiator) in water. The solution is then
30,000 and 50,000 mg/L, respectively. Note that 30,000 ppm cor- sprayed slowly over heated oil maintained at 60 to 80 C (140 to
responds to 250 lbm/1,000 gal in field units, which is not very 180 F). The reaction mechanism of this chemical system is shown
much to use in a field application for a retarder (Al-Muntasheri in Fig. 12. After 30 minutes, the mixture is cooled, the oil is sepa-
et al. 2010). In terms of performance in porous media, in Berea rated and removed, and the microspheres are collected. Note that
cores, the gel reduced the permeability of the core from 47 to 0 the sprayer has different sizes allowing different sizes of the pro-
md at 90 C (194 F). The gel was not aged for more than 1 week duced microspheres. These microspheres can expand up to five
in those tests, yet its strength was investigated in high-pressure times their original size in 5 days when mixed in distilled water.
experiments in which the gel withstood yielding pressures of This expansion process is a function of time and salinity, where
1,000 psi (Al-Muntasheri and Zitha 2009) at room temperature. expansion decreases with increasing salinity. For example, in
The development in this system consisted only of laboratory pro- 20,000 ppm NaCl brine, the microspheres expanded to only twice
totypes, and no field data are available for this system. their original size after 5 days at 78.8 C (175 F).
Chitosan Crosslinked Gels. PEI was phased out from the Nor- The microspheres were reported to have large elastic (storage)
wegian section of the North Sea. Reddy et al. (2003) studied a and viscous (loss) moduli. However, no comparisons were made
replacement for PEI. The gel system was based on chitosan, a with the elasticity of other systems. The elasticity of the micro-
crosslinker that can be extracted from natural resources (Fig. 6) spheres was used to explain the propagation of these materials. It
and that can crosslink a variety of acrylamide-based polymers. was stated that the microspheres deform and recover their shapes
Crosslinking PHPA with chitosan gave lipping gels over the tem- when passing through pore throats. Moreover, a long sandpack
perature range of 65 to 88 C (150 to 190 F) for a weight ratio of (1400 cm) with five pressure taps was used to study the propaga-
14. The system showed fast gelation at 190 F (3 hours) for different tion of these microspheres. The brine permeability of this sand-
formulations. AMPS/Acrylamide showed long gelation time (48 pack was 3,852 md. It was found that the pressure increased in
hours) at 121 C (250 F) at the same weight ratio. No field-applica- Tap 1 first, followed by an increase in the other taps. The authors
tion data are available for this system. Reddy et al. (2003) also used this finding as an indication of the propagation of the micro-
studied the crosslinking of PAtBA crosslinked with chitosan and spheres through the sandpack. It was stated that the microspheres
reported that the data showing a ratio of 14 (PAtBA/PEI) resulted can be dispersed broadly in the pores when injected with water in
in ringing gel at 190 F (88 C) and 5.5-hours gelation time. Chito- a sandstone reservoir. However, in case of stratified reservoirs
san precipitates at a pH of 6. This prevented further developments with crossflow, the propagation of these particles into less-perme-
of this crosslinker and the subsequent field applications. able strata was ignored, which may lead to blocking of pores and
have adverse effects. Moreover, higher salinity (more than 20,000
ppm NaCl) may limit the application because it was found that
Microgels for Deep Modification of Water-Injection Profiles. the expansion of microspheres decreases with increasing salt con-
Although microgel systems were developed as RPMs to reduce tent. Although particles could be produced with the same size,
water production (Chauveteau et al. 2000, 2001, 2003, 2004; pores are not all the same size; therefore, particles may enter all
Feng et al. 2003; Rousseau et al. 2005; Zaitoun et al. 2007; Cozic or most pores. The reader should realize that particles for in-depth
et al. 2009), other systems involving suspensions with various profile modification should be designed small enough to flow
chemical properties were developed for total water shutoff and freely into high-permeability zones and, at the same time, large
deep modification of water-injection profiles. The following two enough not to enter low-permeability zones. In addition, the par-
subsections will provide an overview of two technologies. These ticles should be immobile to divert water into unswept oil zones.
two technologies provide a deep water-shutoff application in This chemical system was applied in Jidong, Dagang, and
high-permeability zones that are responsible for taking most of Shengli oilfield formations in China. The authors reported the
the injected water, resulting in poor reservoir sweep. Thus, the field-application data for a water injector in the Lizuan area.
injected microgels block the high-permeability zones and direct Injection pressure increased after the treatment by 1 to 5 MPa,
water to less-swept zones and help recover additional oil. Table 7 indicating plugging of the water-injection layers. Moreover, the
gives an overview of the technologies reported here. water-injection profile was improved in the well, where the water
PAM/N,N0 -Methylenebisacrylamide Aggregates. Preformed started flowing into seven layers instead of only two layers before
gel aggregates (microspheres) were introduced to provide total the treatment (from water distribution results). The authors
water shutoff with deep penetration into the reservoir. These reported that there is a decrease in the water cut from 55 vol% to
materials are injected in the suspension form with diameters rang- a minimum value of 26 vol% in the producing wells. Overall, a
ing from 10 to 30 lm. Lei et al. (2011) reported on the laboratory total of 6,467 tons of incremental oil was recovered after 7
testing of a microgel crosslinked organically. In addition to the months as a result of this treatment. Wang et al. (2010) studied
controlled size of the produced microspheres, this system is this system for profile modification in sandstone cores with a
thought to provide a short crosslinking time (2 hours). This com- smaller size. The authors were able to produce microgels (nano-
pares with a crosslinking time of 1 week for CDGs that are based spheres) 50 nm in size. In the coreflood experiments, injection of
on crosslinking of PHPA with aluminum citrate (Spildo et al. 0.5 pore volumes of microgel solution containing 1 wt% polymer

February 2014 SPE Journal 143

 NH2 O
Aluminium Persulfate
H2C CH C O + H2C CH C NH CH2
60–80 °C
2

Acrylamide N, N´ methylene bisacrylamide

NH2

C O
CH CH2 CH2 CH
C O
NH n

CH2
NH NH2
C O C O

CH CH2 CH2 CH

Fig. 12—Synthesis of microspheres from acrylamide and N,N 0 -methylenebisacrylamide (Lei et al. 2011).

produced a small amount of oil. Then, the core was immersed in was found that PPGs follow three arrangements. After the injec-
water for 15 hours at 55 C (131 F). This was done to allow the tion of the PPG suspension, it was observed that the particles will
nanospheres to swell and absorb water. The formation-brine injec- move toward the pore throat; then it will be broken into two parts;
tion was then resumed. A 20% incremental recovery of oil was and then the particles will plug two adjacent pores.
realized because of the blockage of the water paths of low resist- The injectivity of PPG was investigated in a pilot test per-
ance by the nanospheres. formed at Shengli oil field, east China (Coste et al. 2000). Two
Another version of acrylamide monomer/N,N0 -methylenebisa- injection wells were selected at Shangdian reservoir. The lithol-
crylamide system was developed in the past decade. This system ogy of this reservoir is sandstone with a high-layer permeability
was designed specifically for oil fields in China. These oil fields ranging from 2 to 6 darcies and low-layer permeability ranging
exhibited high-permeability variations and extreme channels from 0.04 to 0.5 darcies. The water cut of the producers of the
(Coste et al. 2000). This system is referred to as PPG. PPGs have subject wells was above 90%. The data after 8 months of treat-
many advantages over other polymer systems (Bai et al. 2007a). ment showed a decrease in water cut as well as an increase in
Synthesis of PPGs at surface facilities can avoid some drawbacks incremental oil by a total of 2,278 tons. The benefit from the treat-
that may exist with the in-situ gelation systems, such as control- ment in terms of cost was reported to be approximately USD
ling the gelation time and effect of shear on gelation. The size 180,000. Bai et al. (2007b) reported about two field-application
(from micrometers to centimeters) and strength of PPGs are both cases that used PPGs. The first case was in Zhongyuan oil field,
controllable. Because of their size, PPGs were developed only for China. The reservoir is sandstone with an average permeability of
treating fractured reservoirs. PPGs are thermally stable up to 121 md, a temperature of 107 C (225 F), and high formation-
120 C (250 F) and can resist salinities up to 300,000 ppm. The water salinity (15  104 ppm). The treatment resulted in a
produced water can be used to prepare PPGs instead of using fresh decrease in water cut from approximately 80 to 70% and an
water, and this will lead to decreasing the cost of the treatment as increase in oil production from 40 to 60 tons/D. The second case
well as protecting the environment. was in Xingbei oil field in Daqing, China. The reservoir is hetero-
These aggregates were considered superabsorbent crosslinked geneous, with thick oil layers. The reservoir permeability ranges
polymers, which can swell in formation water within the range of up to 1,200 md, with temperature and salinity of approximately
30 to 200 times their original size (Bai et al. 2008). The system is 45 C (113 F) and 4,500 ppm, respectively. The water cut before
prepared by mixing acrylamide monomer, N,N0 -methylenebisa- treatment was more than 90%. The post-treatment results showed
crylamide (organic crosslinker), initiator (peroxydisulfate), and 8% reduction in water cut as well as 2,400 tons more incremental
some other additives (Bai et al. 2007b). The mixture is heated to oil. Bai et al. (2008) reported another case study in Lamadian res-
60 C (140 F) to start the reaction, which completes in 30 minutes, ervoir in Daqing oil field, China. The reservoir is heterogeneous
then is aged for an extra 3 hours at room temperature. The pro- sandstone, with temperature and salinity of approximately 40 C
duced PPG is cut into pieces and dried at 70 C (160 F). The final (104 F) and 4,000 ppm, respectively. The initial average water
step is to grind the particles mechanically before use. Bai et al. cut was 95.4% before treatment. The post-treatment showed a
(2007b) studied some factors that can affect the swelling and the decrease of 0.94% in average water cut, and the oil production
strength of the PPGs. increased by 34.8 tons/D.
PPGs have a limitation to be applied for conformance control. Thermally Activated Microparticles (Bright Water Technology).
PPGs are developed to be used in reservoirs with small fractures A system for modification of injection profile known as Bright
or high-permeability channels, but not for treating matrix. How- Water, which can be injected with water for in-depth waterflood-
ever, PPGs cannot be used in very severe open channels or super- sweep control (Chang et al. 2002), was introduced during the last
high-permeability fractures because they may be flushed out from decade. This thermally activated particle system was developed as
the producers. Bai et al. (2007a) studied the propagation of PPGs a collaboration effort between Chevron, BP, and Nalco in 1997.
through porous media in a sandpack model. Macroscopically, it The particles are created from PAM-based particles crosslinked

144 February 2014 SPE Journal

with an organic, nonlabile crosslinker that controls the size of the that treatment. The thermally activated microparticle technology
particle. The formulation also includes a labile crosslinker that was also implemented in a San Jorge basin sandstone reservoir in
degrades as a function of time and temperature, allowing the par- Argentina (Mustoni et al. 2010). The irregular reservoir sweep was
ticle to be exposed to the surrounding water; the particle then reported to be because of the presence of thief zones with perme-
expands in size (Ohms et al. 2010). The particles will tend to abilities ranging from 500 to 1,000 md. A total of six treatments
block pore throats to water and prevent further fluid flow through was executed in two fields of the San Jorge basin, the Koluel Kaike
the rock. Consequently, injected water will be diverted into less- and Piedra Clavada fields. The post-treatment results showed a
swept zones, which enables more oil recovery. The particles used decrease in WOR from 55 to 39 (30% reduction); at the same time,
in this technology are approximately 0.5 lm in diameter (Rous- oil production increased by 40%. The system was also applied in
sennac and Toschi 2010). They are produced in light mineral oil Alaska with positive results as reported by Ohms et al. (2010). A
with 30% activity. Then, an emulsion is made by adding a surfac- total of 60,000 bbl of oil was produced over a period of 4 years
tant to disperse the particles and emulsify the carrier oil. A spe- compared with a 10-year target of 50,000 to 250,000 bbl. In
cific amount of shear is needed to accomplish the mixing. Chang another attempt, the thermally activated microparticles were tested
et al. (2002) reports detailed chemistry, and an overview of the in Salema field in the Campos basin, Brazil (Roussennac and
chemical components is provided here. The polymer is based on Toschi 2010). The thief zones of the reservoir had permeabilities
AMPS, whereas the labile crosslinker (reversible) includes diacry- ranging from 100 md to darcy-level permeabilities, and the tem-
lamides and methacrylamides of diamines. The stable (nonlabile) perature was 88 C (190.4 F). The incremental oil gain was under
crosslinker is based on methylene bisacrylamide. evaluation by the authors at the time of their paper publication.
Frampton et al. (2004) evaluated the performance of the micro-
particles in a long sandpack (66 ft long) divided into five sections Environmental Issues and Toxicity
with different permeabilities. At the first 50 ft, the pressure differ- An important factor to be considered for the selection of a certain
ence was noticed to be low, indicating that the particles penetrate chemical for water control is the toxicity level of its components.
the sandpacks with no swelling. At the last section of the sandpack, Therefore, in this section, we shed light on some toxicity levels of
the pressure drop increased after approximately 100 days, indicat- some chemicals reported in this paper. One way to measure toxic-
ing the beginning of the expansion process. The authors referred to ity of chemicals is the median lethal dose (LD50), which measures
this as the popping process. Scanning electron microscopy showed the required amount of the material required to kill 50% of
that the particles were enlarged from 0.1 to 3 lm to 2 to 4 lm. The the given test population (mice, for example). For inorganic cross-
authors also reported on the viscosity change of the system as a linkers, Cr3þ is known to have toxicity issues. The toxicity of
measure of its expansion. This viscosity change occurred because Cr3þ compounds depends on the oxidation state. As such, Cr6þ
when the system swells with water, it reduces the volume fraction is more toxic than the trivalent state (i.e., Cr3þ). In addition, Cr6þ
of the continuous phase. This reduction translates into an increase is more easily absorbed by either the inhalational or the oral route.
in viscosity. The data indicated that the viscosity of the system The LD50 value for Cr6þ is 29 mg/kg body weight in rats, whereas
increased with temperature and time. For example, at 210 F the LD50 value for Cr3þ is 11,300 mg/kg of body weight (Assem
(98.89 C), the viscosity increased by a factor of 17 after 45 days. and Zhu 2007). On the other hand, PEI is much less toxic com-
Pritchett et al. (2003) reported the operating limits for the applica- pared with Cr6þ. The LD50 value for PEI is 2,200 mg/kg of body
tion of the thermally activated microparticles: The applicable tem- weight in rats. However, because of European environmental reg-
perature ranges from 50 to 150 C (122 to 302 F), the permeability ulations, PEI was planned to be phased out from the Norwegian
in the thief zone must be greater than 100 md, and the salinity of sector of the North Sea (Reddy et al. 2003). As such, chitosan is
the injected water should be less than 70,000 ppm. It is worth men- being studied for use as a replacement for PEI. It is nontoxic and
tioning that laboratory tests can be used to select the optimum for- biodegradable. A value of LD50 was reported to be 16,000 mg/kg
mulation of the particles because they are available in different of body weight in mice (Reddy et al. 2003).
commercial grades with different chemical properties covering a Isocyanates are very interactive with bases, acids, and alco-
wide range of temperatures (Mustoni et al. 2010). In addition, the hols, and should not be stored near these chemicals. Moreover,
type of labile crosslinker to be used is a function of the temperature isocyanates should be stored in closed containers away from water
of the targeted reservoir. because isocyanate/water reaction can generate enough pressure
The thermally activated microparticle process has a legitimate to rupture containers. Isocyanates are very toxic (Patnaik 2007).
basis for in-depth profile modification, but there are rigid require- For example, the LD50 value for methyl isocyanate is 69 mg/kg of
ments for placement and applicability. As mentioned before, the body weight in rats. For deep profile modification, the N,N0 -meth-
expansion of the microparticles requires sufficient time and ele- ylenebisacrylamide is used as a crosslinker. Its LD50 was reported
vated temperature during their propagation through the rock ma- to be 380 mg/kg of body weight in mice.
trix. This technology has been developed to be applied in hot or
warm reservoirs in which cold water has been injected (Seright Conclusions
et al. 2011). The injection of cold water creates what is called a In this paper, a thorough review on the development of polymer
thermal front. The microparticles should be injected and swell systems for water shutoff over the last 10 years is summarized.
first in the high-permeability zones after passing the thermal front. Various polymer systems were identified. These include organi-
This results in diverting the injected water to less-swept zones cally and inorganically crosslinked polymer gels, resins, and micro-
(low-permeability zones), and thus additional oil could be recov- and nanosphere gels. These systems were applied in oil- and gas-
ered (Chang et al. 2002; Ohms et al. 2010). If the microparticles producing wells as well as water-injection wells.
flow into the low-permeability zones, they will not be in adequate For inorganically crosslinked gels, nanotechnology was intro-
concentration to form a block (Ohms et al. 2010). There are some duced to extend the gelation time of PHPA/Cr3þ systems. Cr3þ is
limitations for the application of those microparticles. First, the sequestered by the particles formed by PEI and DS. Moreover,
swelled microparticles will not help in improving the sweep effi- PHPA/Cr3þ is mixed with foam to block deep wormholes. Copoly-
ciency much beyond the maximum depth of microparticle propa- mers of PAM were also examined for crosslinking with Cr3þ.
gation. The sweep efficiency in the reservoir before the treatment CDGs were developed for in-depth blockage of high-permeability
is supposed to be very poor for the process to work well. The re- zones in heterogeneous reservoirs. It was claimed that these aggre-
sistance factor of the particles should not exceed that for water gates propagate a long distance into the reservoir and provide
and should not increase during microparticle placement. higher resistance factors compared with the polymer without cross-
The first application of the thermally activated microparticle linker. Other experimental studies showed that these systems do
technology was conducted in the Minas field on the island of not have a deep propagation to support this claim.
Sumatra in Indonesia in 2001, as reported by Pritchett et al. For the organically crosslinked gels, a system was developed
(2003). There was reported to be very little incremental oil after by the PDVSA Research and Development Center that can be

February 2014 SPE Journal 145

used at temperatures up to 160 C (320 F). Another organically Success Story. Paper SPE 129848 presented at the SPE Improved Oil
crosslinked gel system for near-wellbore treatments is the PAtBA/ Recovery Conference, Tulsa, Oklahoma, 24–28 April. http://
PEI gel system, which was used in fields with temperatures up to dx.doi.org/10.2118/129848-MS.
160 C (320 F). Other materials were used along with PAtBA/PEI Al-Muntasheri, G.A. and Zitha, P.L.J. 2009. Gel Under Dynamic Stress in
to increase its strength, such as like cement, silica flour, and Porous Media: New Insights Using Computed Tomography. Paper
RSMs. The elongation of gelation time was achieved by adding SPE 126068 presented at the SPE Saudi Arabia Section Technical
retarders, use of a derivatized form of PEI, and the addition of Symposium and Exhibition, AlKhobar, Saudi Arabia, 9–11 May.
polyamino acid to PEI. The chemistry of the polymer was also http://dx.doi.org/10.2118/126068-MS.
altered to elongate the gelation time. This alteration was per- Al-Tolaihy, M. and Bukhari, D.O. 2010. Study on the Optimization of De-
formed through incorporating some bulky groups (such as AMPS) Scaling Operations in Saudi Arabian Khuff Gas Wells. Oral presenta-
to the polymer backbone. tion given at the NACE International Corrosion Conference, San Anto-
Two systems were identified for deep modification of water- nio, Texas, 14–18 March.
injection profiles. The first one is a microgel system formulated Asghari, K., Taabbodi, L., and Dong, M. 2005. A New Gel-Foam System
by crosslinking acrylamide monomers with N,N0 -methylenebisa- for Water Shut-Off Purposes in Wormhole Reservoirs. Paper SPE
crylamide to produce elastic microspheres with controllable size. 97765 presented at the SPE/PS-CIM/CHOA International Thermal
The other is that involving thermally activated microparticles, Operations and Heavy Oil Symposium, Calgary, Alberta, Canada, 1–3
which was designed to treat deep water-injection wells to modify November. http://dx.doi.org/10.2118/97765-MS.
their injection profiles and help in improving the reservoir sweep Assem, L., and Zhu, H. 2007. Chromium-Toxicological Overview. Insti-
efficiency. One advantage of these new particles is that they have tute of Environment and Health. Version 1. http://www.hpa.org.uk/
a density similar to that of water, enabling them to penetrate webc/HPAwebFile/HPAweb_C/1194947362170.
deeper into the reservoir. Bai, B., Hung, F., Liu, Y., et al. 2008. Case Study on Preformed Particle
In the future, we believe that the area of chemical methods for Gel for In-Depth Fluid Diversion. Paper SPE 113997 presented at the
water shutoff can make use of advances in nanotechnology and 2008 SPE/DOE Improved Oil Recovery Symposium, Tulsa, Okla-
address water-production problems in deep reservoirs. There is a homa, 19–23 April. http://dx.doi.org/10.2118/113997-MS.
need for particles that can swell much more than an order of magni- Bai, B., Li, L., Liu, Y., et al. 2007b. Preformed Particle Gel for Conform-
tude to block fractures with very high permeabilities. Moreover, or- ance Control: Factors Affecting Its Properties and Applications.
ganic crosslinkers for high temperature that are accepted in offshore SPE Res Eval & Eng 10 (4): 415–422. http://dx.doi.org/10.2118/
environments are lacking. This should drive research toward more 89389-PA.
environmentally friendly crosslinkers, such as those from naturally Bai, B., Liu, Y., Coste, J.-P., et al. 2007a. Preformed Particle Gel for Con-
occurring materials. There is a need to investigate the effect of the formance Control: Transport Mechanism Through Porous Media. SPE
retarders on the final gel strength in many of the available systems. Res Eval & Eng 10 (2): 176–184. http://dx.doi.org/10.2118/89468-PA.
Bailey, B., Crabtree, M., Tyrie, J., et al. 2000. Water Control. Oilfield
Acknowledgments Review 12 (1): 30–51.
Barclay, D.A., Lawson, K., Mullins, B., et al. 2006. Stand-Alone Coiled-
The authors would like to thank King Abdul-Aziz City for Sci-
Tubing Water Shutoff Operations Reinstate Well on a Normally Unat-
ence and Technology for supporting this research through project
tended Installation. Paper SPE 100132 presented at the SPE/ICoTA
number AT-30-291. King Fahd University of Petroleum and Min-
Coiled Tubing and Well Intervention Conference and Exhibition, The
erals and Saudi Aramco are also acknowledged for their support.
Woodlands, 4–5 April. http://dx.doi.org/10.2118/100132-MS.
In addition, the authors would like to thank the technical
reviewers of this paper for their useful comments. Berkland, C., Cordova, M., Liang, J.T., et al. 2010. Polyelectrolyte Com-
plexes as Delayed Gelling Agents for Oil and Gas Applications. US
Patent No. 7,644,764.
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Control by a Novel Thermally Activated Particle System to Improve mer Flooding With In-Depth Profile Modification. Paper CSUG/SPE
Sweep Efficiency in Mature Waterfloods of the San Jorge Basin. Paper 146087 presented at the Canadian Unconventional Resources Confer-
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148 February 2014 SPE Journal

 Polymer Systems – A Case History from Wafra Ratawi Field, Kuwait. Khalid Saad M. El-Karsani is a lecturer and a PhD candidate
Paper SPE 81447 presented at the SPE Middle East Oil Show, Bah- working for KFUPM. He has worked for the university since 2009.
rain, 9–12 June. http://dx.doi.org/10.2118/81447-MS. El-Karsani holds a BS degree with first class honors, and an MS
Urlwin-Smith, P.L. 1998. Oil and Gas Field Chemicals. US Patent No. 5, degree with honors, both in chemical engineering, from the
University of Gezira, Wad Medani, Sudan. He was awarded
836, 392.
the Senate Prize for academic excellence during his BS
Urlwin-Smith, P.L. 2001. Blocking Composition for Use in Subterrnean degree study. El-Karsani worked as a teaching assistant at the
Formation. US Patent No. 6, 192, 986. University of Gezira from 2003 to 2007, and as a lecturer from
van Eijden, J., Arkesteijn, F., Akil, I., et al. 2004. Gel-Cement, a Water 2007 to 2009.
Shut-Off System: Qualification in a Syrian Field. Paper SPE 88765 pre-
sented at the International Petroleum Exhibition and Conference, Abu Ghaithan A. Al-Muntasheri is a petroleum engineer working for
Dhabi, U.A.E., 10–13 October. http://dx.doi.org/10.2118/88765-MS. the EXPEC Advanced Research Center of Saudi Aramco in
Dhahran, Saudi Arabia. He has been recently assigned to
van Eijden, J., Arkesteijn, F., van Batenburg, D., et al. 2005. Development
work for the United States subsidiary of Saudi Aramco, Aramco
and Field Application of a Shallow Perforation Shutoff System for HP/ Services Company (ASC) in Houston. Al-Muntasheri is the pro-
HT Oil Wells. Paper SPE 94518 presented at the SPE European For- duction technology team leader of ASC. He has been working
mation Damage Conference, Sheveningen, The Netherlands, 25–27 for Saudi Aramco for the last 12 years. Al-Muntasheri holds BS
May. http://dx.doi.org/10.2118/94518-MS. and MS degrees, both with honors, in chemical engineering
Vasquez, J., Civan, F., Shaw, T.M., et al. 2003. Laboratory Evaluation of from King Fahd University of Petroleum and Minerals (KFUPM),
High-Temperature Conformance Polymer Systems. Paper SPE 80904 Dhahran. He holds a PhD degree in petroleum engineering,
presented at the SPE Production and Operations Symposium, Okla- with cum laude honors, from the Delft University of Technol-
homa City, Oklahoma, 22–25 March. http://dx.doi.org/10.2118/80904- ogy, the Netherlands. Al-Muntasheri served as the Chairperson
of the SPE Saudi Arabia Section for the term 2011–12. He also
MS.
served as the Chairperson of the 2011 Annual Technical Sym-
Vasquez, J. and Eoff, L. 2010. Laboratory Development and Successful posium & Exhibition, 15–18 May, in AlKhobar, Saudi Arabia. Al-
Field Application of a Conformance Polymer System for Low, Me- Muntasheri has published more than 26 papers in refereed
dium, and High-Temperature Applications. Paper SPE 139308 pre- journals and international conferences. He has received sev-
sented at the SPE Latin American & Caribbean Petroleum Engineering eral awards, including the 2011 SPE Century Club Award.
Conference, Lima, Peru, 1–3 December. http://dx.doi.org/10.2118/ Al-Muntasheri serves as a technical reviewer for SPE Journal,
139308-MS. Journal of Canadian Petroleum Technology, and for the Ara-
Vasquez, J., Dalrymple, E.D., Eoff, L., et al. 2005. Development and Eval- bian Journal for Science and Engineering. He is a member of
the Society of Rheology in addition to SPE.
uation of High Temperature Conformance Polymer Systems. Paper
SPE 93156 presented at the SPE International Symposium on Oilfield Ibnelwaleed A. Hussein is a professor of chemical engineering
Chemistry, The Woodlands, Texas, 2–4 February. http://dx.doi.org/ and a former assistant director of the Center of Research
10.2118/93156-MS. Excellence in Petroleum Refining and Petrochemicals at
Vasquez, J., Jurado, I., Santillan, A., et al. 2006. Organically Cross-linked KFUPM. The title of his PhD thesis, which won the Canadian So-
Polymer System for Water Reduction Treatments in Mexico. Paper ciety of Rheology Graduate Student Award for the year 1999,
SPE 104134 presented at the First International Oil Conference and was “Molecular Order, Miscibility, and Rheology of Molten Pol-
Exhibition, Cancun, Mexico, 31 August–2 September. http:// yethylenes.” Hussein joined King Fahd University of Petroleum
and Minerals in January 2000. His specialization is in the areas
dx.doi.org/10.2118/104134-MS.
of polymers and rheology with specific interest in structure-
Vega, I., Morris, W., Robles, J., et al. 2010. Water Shut-off Polymer Sys- property relationships. Throughout Hussein’s academic life, he
tems: Design and Efficiency Evaluation based on Experimental Stud- has received many awards, scholarships, prizes, and nomina-
ies. Paper SPE 129940 presented at the 2010 SPE Improved Oil tions at the University of Khartoum, Sudan, and the University
Recovery Symposium, Tulsa, Oklahoma, 24–28 April. http:// of Alberta. Hussein is actively involved in research in the area
dx.doi.org/10.2118/129940-MS. of polymers, with more than 100 refereed journal and confer-
Veil, J.A., Puder, M.G., Elcock, D., et al. 2004. Water from Production of ence publications. He was awarded the “KFUPM Distinguished
Crude Oil, Natural Gas, and Coal Bed Methane. United States Depart- Research Award” in 2005 and 2010. Hussein is the chemical
engineering editor of the Arabian Journal for Science and En-
ment of Energy, National Energy Technology Laboratory, Under Con-
gineering, a member of the editorial board of the Open Petro-
tract W-31-109-Eng-38, 2004. leum Engineering Journal, and a reviewer for many
Wang, L., Zhang, G.C., Ge, J.J., et al. 2010. Preparation of Microgel Nano- international journals in the area of polymers and rheology. He
spheres and Their Application in EOR. Paper SPE 130357 presented at is also a member of the executive board of the Polymer Proc-
the CPS/SPE International Oil & Gas Conference and Exhibition, Bei- essing Society. Hussein’s work experience includes 4 years in
jing, China, 8–10 June. http://dx.doi.org/10.2118/130357-MS. the oil industry in Sudan, 2 years (1992 to 1994) at KFUPM as a
Zaitoun, A. and Kohler, N. 1988. Two-Phase Flow Through Porous lecturer, and approximately 1 year at the University of Alberta
Media: Effect of an Adsorbed Polymer Layer. Paper SPE 18085 pre- as post-doctoral fellow. He has supervised many MS and PhD
sented at the SPE Annual Technical Conference and Exhibition, Hous- students. During his 12 years at KFUPM, the Chemical Engineer-
ing Department awarded Hussein the Faculty Service Award
ton, Texas, 2–5 October. http://dx.doi.org/10.2118/18085-MS.
three times. His work with the Chemical Engineering Club was
Zaitoun, A., Tabary, R., Rousseau, D., et al. 2007. Using Microgels To Shut acknowledged by awards from the Deanship of Student
Off Water in a Gas Storage Well. Paper SPE 106042 presented at the Affairs. He holds a PhD degree from the Chemical and Materi-
2007 SPE International Symposium on Oilfield Chemistry, Houston, als Engineering Department at the University of Alberta,
Texas, 28 February–2 March. http://dx.doi.org/10.2118/106042-MS. Canada.

February 2014 SPE Journal 149