Journal of Petroleum Science and Engineering 26 Ž2000.

1–10
www.elsevier.nlrlocaterjpetscieng

A review of thermally stable gels for fluid diversion

in petroleum production
Ahmad Moradi-Araghi
103 GB Philips Research Center, Phillips Petroleum Company, BartlesÕille, OK, USA

Received 12 December 1998; accepted 15 December 1999

Abstract

The use of water-soluble polymers coupled with proper concentration of cross-linkerŽs. as flow-diverting agents have
become a common practice in recent years for oil recovery applications. In such practice a solution containing the polymer
and cross-linkerŽs., referred to as gelant, is injected in desired zones and allowed sufficient time to set into a solid gel. These
gels are used in injection wells to divert the flow of injected water or gas ŽCO 2 . to un-swept zones where additional oil can
be recovered. The gels are also used to shut off the flow of water that strongly interferes with hydrocarbon production and
substantially reduces the profitability of wells. There are a number of gelling systems available for treatment of lower
temperature reservoirs. However, gels that can tolerate the harsh conditions of elevated temperatures and high salinity and
divalent cations commonly present in deeper reservoirs are limited. When high molecular weight polyacrylamides are
cross-linked to treat these hot reservoirs, their acrylamide groups will thermally hydrolyze. The resulting gel will further
cross-link with the divalent cations available in the media, shrinking it to a fraction of its original volume. This process,
which is referred to syneresis, can be avoided by selection of acrylamide-based polymers that are protected from extensive
thermal hydrolysis. While other remedies such as lower-molecular-weight polyacrylamides, retarding agents or cooling of
the target zones are attempted; these options often create unintended results. Recent studies include gelation of high
molecular weight polyacrylamides with hydroquinone ŽHQ. and hexamethylenetetramine ŽHMTA. or terephtalaldehyde,
terphthalic acid with hyroquinone, dihydroxynaphthalene and dibasic esters. These gelling systems are often prepared in
seawater and require 2% sodium bicarbonate for their stability. Due to health and environmental concerns, the use of
compounds such as HQ and formaldehyde is discouraged. Other recent studies describe the use of a modified polyacryl-
amide with polyethyleneimine. While the resulting gels are stable, their use is prohibitive due to requirement of a large
polymer content Ž3- to 7-fold., as well as the high price of chemicals needed. This paper reviews the gelling systems
available for high temperature well treatments. q 2000 Elsevier Science B.V. All rights reserved.

Keywords: thermally stable gels; fluid diversion; petroleum

1. Introduction and gas. These systems, which are typically com-

posed of a water-soluble polymer and cross-linkerŽs.,
The use of gelling systems as diverting agents is are dissolved in water and injected into the target
widely practiced today to improve production of oil zones. After allowing sufficient time, the injected

0920-4105r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 Ž 0 0 . 0 0 0 1 5 - 2
2 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
gelling solution, referred to as AgelantB, sets into a
solid mass, which behaves as flow diverting or
blocking agent. Gels are used in treatment of injec-
tion and production wells. In the injection well treat-
ments, the gelant is placed into high permeability
channels andror fractures. This application is re-
ferred to as profile modification, in which the in-
jected gelant in target zones are set into a solid mass,
diverting the flow of injected water or gas to un-swept
zones.
Production well treatments involve injection of
the gelants into the fractures or high-permeability
zones that produce a lot of water, thereby reducing
oil production. The source of water could be an
aquifer underlying the productive zone or
channelsrhigh permeability Athief zonesB in direct
communication with the injection wells. This appli-
cation not only improves drawdown from the pro-
ductive zones; it also reduces or eliminates the cost
associated with lifting, separation, treatment and dis-
posal of produced water.
Selection of the gel for a given well treatment
strongly depends on reservoir conditions such as
temperature, salinity, hardness and the pH of the
water used for preparation of the gelant. Other pa-
rameters to be considered for the proper selection of
a given gelant include salinity of the formation wa-
ter, permeability of the target zone, and the lithology
of the formation.
Fig. 1. Precipitation times for 1000 ppm originally unhydrolyzed polyacrylamide aged in various brines.
There are a number of gelling systems available
for improved oil recovery ŽIOR. applications. The
most common polymers used for gel treatment of
petroleum reservoirs are polyacrylamides with vary-
ing degrees of hydrolysis Žcharge densities. and
molecular weights. These polymers are typically in-
expensive and can be cross-linked with metallic and
organic cross-linkers to produce suitable gels
ŽMoradi-Araghi et al., 1988.. A typical gel consists
of about 0.7–1.0% polymer and 500–2000 ppm
cross-linker with the remainder being water Ž; 99%..
The gels produced with polyacrylamides can be used
for treatment of the reservoirs with temperatures
below 758C. In hotter reservoirs, the acrylamide
groups of the polymer hydrolyze to carboxylate
groups ŽMoradi-Araghi and Doe, 1984., which can
over-cross-link with divalent cations such Caq2 and
Mgq2 commonly present in their environment
ŽAhmed and Moradi-Araghi, 1994.. Fig. 1 shows a
plot of precipitation time versus hardness level for a
solution of 1000 ppm polyacrylamide, which was
originally unhydrolyzed. As the polymer thermally
hydrolyzes, it produces carboxylate groups that
cross-link with the divalent cations present in water
and precipitate out of solution. This behavior is
observed in the absence of a primary cross-linking
system. The gels produced with polyacrylamide and
cross-linking systems, however, are not protected
against thermal hydrolysis. The carboxylate groups
 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
produced by thermal hydrolysis additionally cross-
link with divalent cations. The process of over-
cross-linking results in expulsion of water from the
gel structure, shrinking its volume to a large extent.
This phenomenon is referred to as gel syneresis. This
paper reviews the gelling systems that can be used to
treat wells in high-temperature reservoirs.
2. Discussions
Currently, there are a few gelants available which
can be used under hostile environmental conditions.
The polymers used in these gelants include low
molecular weight polyacrylamides, natural polymers,
and special polymers designed to tolerate such condi-
tions. Metallic cross-linkers can be used to produce
gels with anionic polymers. This is done through
formation of the ionic bonds between multivalent
cations and the negative sites of the polymer. The
gels produced through metallic cross-linkers typi-
cally have lower thermal stability. Organic cross-lin-
king involves the formation of covalent bonds be-
tween functional groups of the polymer, i.e. amides,
and the cross-linker, connecting two or more poly-
mer chains. To obtain thermally stable gels, one
needs to start with thermally stable polymer ŽAhmed
and Moradi-Araghi, 1996.. Details on various gela-
tion processes follow.
2.1. Metallic cross-linking of polyacrylamides
Commercially available acrylamide polymers
come in three forms: anionic Žcontain negative
charges on polymer backbone., neutral, or cationic
Žcontain positive groups on the polymer backbone..
In general, both anionic and cationic polyacryl-
amides contain a significant amount of neutral acy-
lamide groups. Anionic polyacrylamides can be
cross-linked with multivalent cations such as Crq3 ,
Alq3 or Zrq4 to produce gels. The rate of cross-lin-
king and gel formation strongly depends on the
charge density of the polymer as well as the source
of tri- or tetravalent cations. Other factors affecting
the rate include temperature, pH, salinity and the
concentration of polymer and cross-linker. Complex
forms of metallic cations are the best sources for
3
these cross-linkers. This is done to reduce the rate of
reaction between the cation and the polymer. For
example, chromium chloride cannot be used directly
to form suitable gels with anionic polyacrylamides
due to its fast reaction. However, chromium acetate
or chromium propionate is used to produce good gels
with plenty of time to place the gelant in desired
zones in the formation before setting ŽMumallah,
1988; Mumallah and Shioyama, 1987; Wu and Mu-
mallah, 1985; Wu and Mumallah, 1986.. The result-
ing gels are suitable for lower temperature reservoirs.
At elevated temperatures Ž) 908C. the rate of gela-
tion of high molecular weight polymers with
chromium acetate or propionate is too fast for plac-
ing the gelant in the target zones. Furthermore, ther-
mal hydrolysis of the acrylamide groups ŽMoradi-
Araghi and Doe, 1984. on the polymer produce
additional cross-linking sites for interaction with
Caq2 and Mgq2 , resulting in syneresis of the gels.
To avoid such problems, Sydansk Ž1990. suggests
the use of lower-molecular-weight polyacrylamides
Ž270,000 Mw. with low anionic charge cross-linked
with chromium ŽIII. acetate. The onset of gelation
for this system at 123.98C was not observed until
after 5 h of aging. However, the polymer concentra-
tion for this system was 5%, substantially higher
than 0.7–1.0% with the high molecular weight
Ž10,000,000–15,000,000 Mw . polyacrylamides.
Sydansk Ž1995. also varies the ratio of the carboxyl-
ate groups to CrŽIII. concentration to retard the rate
of gelation.
Lockhart and Albonico Ž1992. reported on the
gelation of high molecular weight polyacrylamides
with CrŽmalonate. 3 at elevated temperatures. Their
results indicate that gelation times with this system
are orders of magnitude longer than with CrŽacetate. 3 .
They also observed that addition of uncomplexed
malonate ions to the gelants, results in the gelation
times with two orders of magnitude longer than
systems without free ligands.
Albonico et al. Ž1993. and Bartosek et al. Ž1994.
reported on the use of various retarding agents such
as glycolates, salicylates and malonates to reduce the
rate of gelation with the high molecular weight
polyacrylamides. These retarding agents further im-
prove the propagation of CrŽIII. ions into the forma-
tion However, addition of gel retarding agents also
results in the formation of weaker gels.
4 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
A recent study by Bryant et al. Ž1996. indicates
that gel syneresis in treated matrix might not create a
substantial problem. This study indicates that even
gels, which synerese extensively in porous media,
might still be effective in permeability reduction to a
large extent. This paper, however, cautions against
the use of the gels vulnerable to syneresis for treat-
ment of fracture zones.
Albonico and Lockhart Ž1993. described the use
of low molecular weight complexing agents such as
citrate, oxalate, salicylate, lactate, tartarate, EDTA,
etc. to prevent syneresis of gels. These compounds
are used to complex with the divalent cations such as
Caq2 and Mgq2 to passivate them so they can not
cause syneresis of the gel due to over cross-linking
carboxylate sites with these cations. This study re-
vealed that an acrylamide-based polymer dissolved
in seawater and cross-linked with phenol and formal-
dehyde at 1208C syneresed about 10% in 4 days of
aging. However, the same gelant containing 0.1 M of
oxalate took over 365 days to reach 10% of syneresis
under identical conditions. The low solubility of
Caq2 –oxalate complex, however, might limit its ap-
plicability in matrix treatments. It should also be
mentioned that maintaining the integrity of these
gelant packages due to chromatic separation in the
reservoir should be of concerns to their application.
2.2. Organic cross-linking of polyacrylamides
Hutchins et al. Ž1996. described the application of
a new high-temperature organic cross-linking system
suitable for high temperature gel treatments. This
cross-linking system believed to be a combination of
hydroquinone ŽHQ. and hexamethylenetetramine
ŽHMTA. is used in seawater in combination with 2%
sodium bicarbonate. The polymer used in this pro-
cess is polyacrylamide, eliminating the need for the
more expensive thermally stable polymers. The role
of sodium bicarbonate in addition to pH control is to
soften the water by precipitating the divalent cations
present in seawater. The resulting gels were shown
to be stable for 12 months at 1498C and 5 months at
176.78C. This gelling system has been applied in
four well treatments. The first two treatments in-
volved the use of these gels for abandoning some
perforations. In one application, this gel was selected
in place of cement due to its improved strength and
anticipated lifetime. In the second case, the gel was
used to treat a watered-out gas zone due to its lower
cost in comparison to squeeze cementing. Both treat-
ments were successful. In the first treatment 1095
bbls of gel was used to block an upper zone that was
producing a lot of water. This well treatment resulted
in 660 bopd and 1490 bwpd as compared to 340
bopd and 3760 bwpd prior to the treatment.
The other two treatments described in this paper
dealt with water control in the gas wells. In these
treatments, gelants were injected in stages alternated
with slugs of nitrogen to maintain the permeability
of gas while reducing the permeability to water. A
gas well located in New Mexico with a bottomhole
temperature of 1218C was treated with 620 bbls of
the gelant. The last slug of gelant was displaced from
the wellbore with nitrogen. This treatment resulted in
60% reduction in water production with no increase
in gas production. In a second treatment, a package
of three Canadian gas wells with a bottomhole tem-
perature of 112.88C was successfully treated with
this gel, resulting in a 315% increase in gas produc-
tion with 65% reduction in water production.
In one recent study, Dovan et al. Ž1997. described
the application of several new cross-linking systems
that can be used at higher temperatures. These sys-
tems produce gels at slow rate suitable to treat very
hot wells. One cross-linking system exhibited a gel
time of several days at 176.78C. The combination of
HQ and HMTA as described in the previous paper,
produces the best results with cationic polyacryl-
amides. This paper ŽDovan et al., 1997. reported on
gelation of polyacrylamides with a number of new
cross-linkers that include terephtalaldehyde, tereph-
thalic acid, dihydroxynaphthalene, glutaric acid, gal-
lic acid and dibasic esters. The authors designated
HMTA, terephtalaldehyde, terephthalic acid and glu-
taric acid as primary cross-linkers, while HQ, dihy-
droxynaphthalene and gallic acid are named sec-
ondary cross-linkers ŽDovan et al., 1997.. In such
classification, primary cross-linkers are those com-
pounds that can produce gels with the polymer by
themselves; however, the resulting gels are often
unstable. The secondary cross-linkers have little or
no gelation properties by themselves. However, they
stabilize the gels produced with the primary cross-
linkers at elevated temperatures. Because of its lower
 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
toxicity to aquatic life, dihydroxynaphthalene is pre-
ferred over HQ.
While extensive laboratory data is presented
ŽDovan et al., 1997., showing thermal stability for
the resulting gels, none of the new systems reported
in this paper were tested in the field. Aging results
for the gels produced with terephthalaldehyde at
176.78C suggest it has potential for application at
elevated temperatures.
2.3. Organic cross-linking of acrylamide-based poly-
mers
There are a number of publications ŽHsieh and
Moradi-Araghi, 1991; Hsieh et al., 1992; Clampitt et
al., 1993; Moradi-Araghi et al, 1993; Albonico et al.,
1995; Bryant et al., 1997. dealing with gelation of
acrylamide-based polymers with phenol and formal-
dehyde cross-linking systems. The polymers used in
these studies are thermally stable under harsh envi-
ronmental conditions. This is accomplished by inclu-
sion of other monomers into the polymer structure,
which limit thermal hydrolysis of the acrylamide
groups ŽMoradi-Araghi et al., 1987.. Another option
is to use polyacrylamides but with substantially lower
molecular weight. In the later case, even though the
polymer will hydrolyze to a large extent, the result-
ing gels will not synerese. This is due to the solubil-
ity of the complexes formed between divalent cations
and the low molecular weight polyacrylic acids
Fig. 2. Gelation of 1% polymer cross-linked with phenol and formaldehyde at 1218C.
5
ŽChang, 1983., produced as a result of thermal hy-
drolysis.
Extensive studies in our laboratories ŽMoradi-
Araghi et al., 1993., showed that the gels produced
with thermally stable acylamide-based polymers dis-
solved in seawater and cross-linked with phenol and
formaldehyde, are very stable. Fig. 2 shows a plot of
percent GS Žgel strength. versus time for a gel
produced with 1% of a thermally stable polymer
cross-linked with phenol and formaldehyde. This gel
prepared in seawater has survived over 13 years of
aging at 1218C. This gelling system has been applied
in a number of well treatments with successful re-
sults. Unlike the metallic cross-linking that occurs
between the carboxylate groups of the polymer and
the multivalent cations, these gels are the result of
cross-linking between the acrylamide groups and
phenol–formaldehyde reaction product. Fig. 3 shows
the proposed gelation mechanism for this system.
Evaluation of these gelants in porous media ŽBryant
et al., 1997. indicates good injectivity in core floods
and slim tube experiments up to 1408C. However,
portioning of phenol into the crude oil might be an
impediment to propagation of the gelants. The use of
a phenol pre-flush was shown to solve this problem
based on the results from a numerical modeling
study.
A major problem associated with the use of phe-
nol–formaldehyde cross-linking system is the toxic-
ity of phenol and especially the carcinogenic charac-
6 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
Fig. 3. Gelation mechanism.
ter of formaldehyde. Because of environmental con-
cerns as well as the safety of workers performing
these treatments, we undertook a study ŽMoradi-
Araghi, 1994. searching for alternative cross-linkers
with lower toxicity that can produce stable gels. This
study identified several compounds that can be used
in place of phenol ŽMoradi-Araghi, 1990, 1991, 1993,
1995; Moradi-Araghi and Stahl, 1991, 1992.. These
compounds include o- and p-aminobenzoic acids,
m-aminophenol, phenyl acetate, phenyl salicylate,
salicylamide, salicylic acid and furfuryl alcohol.
However, only one compound, HMTA, can be used
in place of formaldehyde to produce stable gels.
2.4. Gelation of acrylic ester r acrylic acid copoly-
mer
Morgan et al. Ž1997. reported on the gelation of
copolymers of acrylamide and tertiary butyl ester of
acrylamide. In one scheme, the ester groups are
hydrolyzed to acrylic acid groups and cross-linked
with CrŽIII. ions. In another method, these polymers
are cross-linked with polyethyleneimine to produce a
thermally stable gel. In such process, the amine
groups perform nucleophilic attack at the ester sites
of various polymers producing a cross-linked cova-
lent bond. This process produces gels that are stable
at elevated temperatures. Bulk gel testing and core
flood results showed that the resulting gels survived
months of aging at 1568C. However, the rate of
gelation for this process becomes too fast to be
suitable for temperatures above 938C. In such condi-
tions, the treatment area is cooled down to below
908C through the injection of cold water. However,
this is undesirable due to stress cracking of the rock
and creation of additional channels. The gels pro-
duced by this system require a large polymer concen-
tration Ž5–10%.. This requirement, coupled with the
high price of the polymer prohibits the use of this
gelling system in most treatments. Hardy et al. Ž1998.
reported on the propagation of these polymers organ-
ically cross-linked with polyethyleneimine. These
gelants can propagate eight times farther than
chromium-based gelants under equivalent conditions.
Stainless steel tubes ŽID s 1.60 cm, lengths 2.0 m.
filled with crushed Berea, silica or silicarcarbonate
blend were treated with one pore volume of this
gelant. After allowing sufficient time for curing, the
performance of the gels was evaluated. In almost all
cases, residual resistance factor ŽRRF. values re-
mained the same throughout the entire length of the
tube. This study compared the results for the tests
performed with one pore volume of the gelant for
this polymer organically cross-linked with polyeth-
yleneimine or a solution of 5% polyacrylamide
cross-linked with chromium propionate. While the
new system propagated between 90–100% into the
sandpack, the gelant made with chromium and poly-
acrylamide only penetrated 50% into the pack. This
paper reported on a method by which the gelation
time and temperature was used to calculate the pump
times and shut-in times for various stages of a well
treatment.
2.5. Production of gels with monomeric compounds
Chang et al. Ž1985. reported on production of a
gelant for high-temperature applications. This gelant,
which is a synthetic thermosetting material, is be-
lieved to consist of resorcinol and formaldehyde. Its
gelation rate can be controlled over the range of
several hours to about 10 days at temperatures of up
to 1058C. The advantage of such gelant is its water-
like viscosity, which makes it desirable for gel treat-
ments. However, this gelling system is very sensitive
to the pH of the water and can only be used in
limited applications. A single injector at 91.78C,
treated with 2000 bbls of this gelant, resulted in
 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
diversion of injection water to the productive zones
with increased oil recovery that was sustained for
several months.
2.6. Gelation of natural polymers
Nagra et al. Ž1986. reported on gelation of natu-
rally occurring polymers for high-temperature appli-
cations. They defined a gel half-life, the time re-
quired for the gel to shrink by 50% at the test
conditions. The results showed a half-life of about
1–45 days for the gels aged at 908C. The gels
produced with 625 ppm scleroglucan, a thermally
stable polymer ŽKalpakci et al., 1990; Rivenq et al.,
1989., with 50 ppm CrŽIII. showed a half-life over
100 days at this temperature. It is suspected that the
gels produced with higher polymer concentrations
Ž5000–10,000 ppm. will perform better. These poly-
mers, however, are very expensive to produce and
have not been tested in actual well treatments. The
gels produced with 3000 ppm xanthan, a biopolymer
with limited thermal stability ŽSeright and Henrici,
1986., and 50 ppm CrŽIII., resulted in a half-life of
50 days ŽNagra et al., 1986..
Nagra et al. Ž1986. also reported on the gelation
of lignosulfonates, a by-product of paper industry
with CrŽIII. at 908C. Solutions of 2% lignosulfonates
cross-linked with 0.5% to 5.0% CrŽIII. retained over
90% of their original volumes in 10 weeks of aging.
Even though lignosulfonates are very inexpensive,
the use of this gelant is economically prohibitive due
to the need for a large concentration of chromium.
Kumar et al. Ž1997. reported on pH dependency
of the gels produced with lignosulfonates. The result-
ing gels were not stable in limestone reservoirs. This
study identified an additive that stabilized the result-
ing gels for application under Bombay High Reser-
voir conditions. These gels were found to reduce the
permeability of the watered-out zones by 95%, with-
out affecting the permeability of the oil-bearing
zones. The authors recommended the use of this
gelling system for the injection and the producing
wells.
Nagra et al. Ž1986. also reported on gelants pro-
duced with phenol and formaldehyde mixtures. This
system, which requires fresh water or low salinity
brines, can survive exposure to divalent cations after
setting. The authors presented data on gelation of
7
1.0% and 3.0% phenolrformaldehyde mixture that
survived over 3 months of aging at 908C and expo-
sure to reservoir brine without an appreciable synere-
sis. While this system is desirable due to its low
viscosity and its thermal stability, concerns over
environmental effects might prohibit its use.
Strom et al. Ž1989. reported on a new extracellu-
lar biopolymer produced by Alcaligenes bacteria.
This polymer can be cross-linked with CrŽIII. to
produce firm gels stable at elevated temperatures. It
can also be gelled at 2000–4000 ppm polymer con-
centration in high salinity brine Ž; 20% TDS. with-
out the need for CrŽIII. ions. Experiments performed
in brines of various salinity and hardness indicated
that Naq ions were a key factor in self-cross-linking
of Alcaligenes biopolymer. Gel samples produced
with this polymer have survived over 2 years of
aging at 748C and 938C. While these gels could be
formed over a wide range of pH values, the best
long-term stability was observed in a pH range of
7–8.
Sampath et al. Ž1989. reported on the use of the
new Alcaligenes biopolymer in profile modification
treatment of four injection wells in South East
Bradley AAB Unit in Oklahoma. A total of 25,300
bbls of polymer without cross-linker was injected
into the four candidate wells. Radioactive profile
logs and pressure fall-off tests performed on all wells
before and after polymer treatment showed positive
response to the treatment. The percentage of the
perforated payzone receiving water increased by 25–
50% in three of the wells. Oil production rate in-
creased above the baseline soon after initiation of
polymer injection. The production rates continued to
increase with time. In 5 months following the treat-
ment, oil production rate was higher about 35%. It
was concluded that polymer treatment successfully
modified vertical and areal sweep efficiency of the
pattern. In 1 year following the treatment, this pro-
ject resulted in an incremental oil recovery of ap-
proximately 25,000 bbls, corresponding to about 0.8
bbls of oil per pound of polymer injected.
2.7. Cross-linking of polyÕinyl alcohol
Polyvinyl alcohol ŽPVA., a commercially avail-
able polymer prepared from polyvinyl acetate, can be
cross-linked to produce thermally stable gels. Hoskin
8 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10

Table 1
Summary of thermally stable gels
Polymer
Polyacrylamides, low Mw
Polyacrylamides, high Mw
Polyacrylamides, high Mw
Polyacrylamides, high Mw
Polyacrylamides, high Mw
Acrylamide-based thermally
Acrylamide-based thermally
stable polymers
Acrylic esterracrylic acid
copolymer
Resorcinol
Scleroglucan
Lignosulfonate
Alcaligenes biopolymer
PVA
PVA-polyvinylamide
copolymer
Cross-linker
CrŽIII. acetate
CrŽIII. malonate
Phenol and formaldehyde
Hydroquinone and hexameth-
ylenetetramine
Terephthalaldehyde, dihydroxy-
naphthalene, HMTA, etc.
Phenol and formaldehyde
stable polymers
Phenyl acetate, phenyl salicy-
late, etc. with HMTA
Polyethyleneimine
Formaldehyde
CrŽIII.
CrŽIII.
Naq
Phenol and aldehyde
Dialdehydes or polyaldehydes
Comments
5% or more polymer needed
Slower gelation rate than with
CrŽIII. acetate
Ligands such as citrate, oxalate,
lactate stabilized the gel
2% sodium bicarbonate needed
for softening and stability
Stable gels
Stable gels
Stable gels, lower toxicity than
phenol and formaldehyde gels
Stable gels. Require large con-
centration and cooling to below
938C
Water-like viscosity of gelant is
a plus. Toxicity is a problem
Stable gels, the polymer is very
expensive
Expensive gels due to high Cr
requirement
Stable gels in pH range of 7–8
High concentration of polymer
and crosslinkers needed
Not widely used
Reference
Sydansk, 1995
Lockhart and Albonico, 1992
Albonico and Lockhart, 1993
Hutchins et al., 1996
Dovan et al., 1997
Moradi-Araghi et al., 1993
Moradi-Araghi, 1994
Morgan et al., 1997
Chang et al., 1985
Nagra et al., 1986
Nagra et al., 1986
Strom et al., 1989
Hoskin and Shu, 1989
Shu, 1997

and Shu Ž1989. reported on gelation of this polymer
with a phenolic component and an aldehyde compo-
nent. Solutions containing 7.5% PVA cross-linked
with about 8% each of phenol and formaldehyde
produced a gel which syneresed about 5% after 10
weeks of aging at 204.48C. Shu Ž1997. reported on
the gelation of PVA-co-polyvinylamide with a di-
aldehyde or polyaldehyde which produced thermally
stable gels. While there are a few patents on the use
of polyvinyl alcohol and their derivatives to produce
thermally stable gels, these systems are not widely
used in gel treatments of wells.
3. Conclusions
wide selection of polymers and cross-linker, which
produce acceptable gels. Selection of a given gelant
strongly depends on temperature, salinity and hard-
ness level of the water used for polymer preparation
as well as the lithology of the reservoir. Other factors
that affect the selection of a gelant include the type
of conformance problem as well as the cost of such
treatment. To insure a successful treatment, one needs
to thoroughly evaluate the gelling system of the
choice in the laboratory before using it in the field.
Furthermore, it is strongly recommended that the
gelling system be tested on site with the water and
all chemicals to be used in the field before the gel
treatment is commenced.

As summarized in Table 1, there are a number of Acknowledgements

gelling systems available that can tolerate the hostile
environments of high salinity, high hardness and The author expresses his gratitude to the manage-
elevated temperatures encountered in deeper reser- ment of Phillips Petroleum for permission to publish
voirs. The systems reported in this paper include a this paper.
 A. Moradi-Araghir Journal of Petroleum Science and Engineering 26 (2000) 1–10
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